U.S. patent number 10,059,880 [Application Number 14/330,247] was granted by the patent office on 2018-08-28 for polymerizable liquid crystal composition and optical anisotropic film.
This patent grant is currently assigned to JNC CORPORATION, JNC PETROCHEMICAL CORPORATION. The grantee listed for this patent is JNC CORPORATION, JNC PETROCHEMICAL CORPORATION. Invention is credited to Yoshiharu Hirai.
United States Patent |
10,059,880 |
Hirai |
August 28, 2018 |
**Please see images for:
( Certificate of Correction ) ** |
Polymerizable liquid crystal composition and optical anisotropic
film
Abstract
A subject is a polymerizable liquid crystal composition in which
tilt alignment is easily developed and an optical anisotropic film
obtained therefrom. A solution is a polymerizable liquid crystal
composition containing one or more polymerizable liquid crystal
compounds selected from compounds represented by formulas (1-1),
(1-2) and (1-3), and a polymerizable liquid crystal compound
represented by formula (2-1). In the following formula, for
example, Z.sup.11 and Z.sup.12 are hydrogen; W.sup.1 is
independently hydrogen, fluorine or a methoxy; W.sup.2 and W.sup.3
are independently hydrogen or methyl; X.sup.1 is independently a
single bond or --CH.sub.2CH.sub.2--; and for example, W.sup.4 is
methyl; and X.sup.2 is --O--; and m1, m2, n1 and n2 are 2 to 15.
Moreover, Z.sup.21 is hydrogen or methyl; R.sup.1 is an alkyl
ester-containing substituent; W.sup.5 is hydrogen; X.sup.3 is
--COO--; X.sup.4 is --O--, for example; and m3 is 2 to 15 and q1 is
0 to 2. ##STR00001##
Inventors: |
Hirai; Yoshiharu (Ichihara,
JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
JNC CORPORATION
JNC PETROCHEMICAL CORPORATION |
Tokyo
Tokyo |
N/A
N/A |
JP
JP |
|
|
Assignee: |
JNC CORPORATION (Tokyo,
JP)
JNC PETROCHEMICAL CORPORATION (Tokyo, JP)
|
Family
ID: |
52390239 |
Appl.
No.: |
14/330,247 |
Filed: |
July 14, 2014 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20150029446 A1 |
Jan 29, 2015 |
|
Foreign Application Priority Data
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|
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Jul 29, 2013 [JP] |
|
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2013-156736 |
May 30, 2014 [JP] |
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2014-113192 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K
19/32 (20130101); C09K 19/56 (20130101); C09K
19/2007 (20130101); G02F 1/13363 (20130101); G02B
5/30 (20130101); C09K 2019/0448 (20130101); G02B
5/3083 (20130101); G02F 2001/133633 (20130101); C09K
2019/2078 (20130101) |
Current International
Class: |
G02F
1/1333 (20060101); C09K 19/32 (20060101); C09K
19/20 (20060101); C09K 19/56 (20060101); G02B
5/30 (20060101); G02F 1/13363 (20060101); C09K
19/04 (20060101) |
Field of
Search: |
;252/299.62
;428/1.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2001-055573 |
|
Feb 2001 |
|
JP |
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2006-307150 |
|
Nov 2006 |
|
JP |
|
2008-134530 |
|
Jun 2008 |
|
JP |
|
2008-138142 |
|
Jun 2008 |
|
JP |
|
2009-286885 |
|
Dec 2009 |
|
JP |
|
2012-177087 |
|
Sep 2012 |
|
JP |
|
Primary Examiner: Visconti; Geraldina
Attorney, Agent or Firm: Greenblum & Bernstein,
P.L.C.
Claims
What is claimed is:
1. A polymerizable liquid crystal composition, comprising component
(A) being at least one compound selected from the group of
compounds represented by formula (1-1), formula (1-2) and formula
(1-3), and component (B) being at least one compound selected from
the group of compounds represented by formula (2-1): ##STR00080##
wherein, Z.sup.11is independently hydrogen, fluorine, methyl or
trifluoromethyl; W.sup.1 is independently hydrogen, fluorine or a
methoxy; W.sup.2 and W.sup.3 are independently hydrogen or methyl;
X.sup.1 is independently a single bond or --CH.sub.2CH.sub.2--;
Z.sup.12 is independently hydrogen, fluorine, methyl or
trifluoromethyl; W.sup.4 is hydrogen, methyl, straight-chain alkyl
having 1 to 7 carbons, branched alkyl having 1 to 7 carbons,
--COORa where Ra is straight-chain alkyl having 1 to 7 carbons, or
--CORb where Rb is straight-chain alkyl having 1 to 15 carbons;
X.sup.2 is --O--; and m1, m2, n1 and n2 are independently an
integer from 2 to 15: ##STR00081## wherein, Z.sup.21 is hydrogen or
methyl; R.sup.1 is a substituent containing an alkyl ester selected
from --R.sup.d--COOR.sup.c, --R.sup.d--OCOR.sup.c or
--R.sup.d--CH.dbd.CH--COOR.sup.c; wherein R.sup.c is straight-chain
alkyl having 1 to 20 carbons, and R.sup.d is a single bond or
straight-chain alkylene having 1 to 10 carbons; W.sup.5 is
independently hydrogen, fluorine or a methoxy; X.sup.3 is
independently a single bond, --COO--, --OCO--,--OCO--CH.dbd.CH--,
--CH.dbd.CH--COO--, --OCO--CH.sub.2CH.sub.2--or
--CH.sub.2CH.sub.2--COO--; X.sup.4 is a single bond, --O--,
--COO--, --OCO----OCO--CH.dbd.CH--, --CH.dbd.CH--COO--or
--OCO--CH.sub.2CH.sub.2--; m3 is an integer from 2 to 15; and q1 is
0 to 2.
2. The polymerizable liquid crystal composition according to claim
1, wherein, in formula (1-1) to formula (1-3), Z.sup.11 is
independently hydrogen or methyl; W.sup.1 is independently hydrogen
or fluorine; Z.sup.12 is independently hydrogen or methyl; and in
formula (2-1), R.sup.c in R.sup.1 is straight-chain alkyl having 1
to 10 carbons; W.sup.5 is independently hydrogen or fluorine; and
X.sup.4 is a single bond, --O--, --COO--, --OCO--CH.dbd.CH-- or
--CH.dbd.CH--COO--.
3. The polymerizable liquid crystal composition according to claim
1, wherein, in formula (1-1) to formula (1-3), Z.sup.11 is
independently hydrogen or methyl; W.sup.1 is independently hydrogen
or fluorine; W.sup.2 is hydrogen and W.sup.3 is methyl; Z.sup.12 is
independently hydrogen or methyl; and in formula (2-1), R.sup.c in
R.sup.1 is straight-chain alkyl having 1 to 10 carbons; W.sup.5 is
independently hydrogen or fluorine; and X.sup.4 is a single bond,
--O--, --COO--, --OCO--CH.dbd.CH-- or --CH.dbd.CH--COO--.
4. The polymerizable liquid crystal composition according to claim
1, wherein, in formula (1-1) to formula (1-3), Z.sup.11 is
independently hydrogen or methyl; W.sup.1 is independently hydrogen
or fluorine; W.sup.2 and W.sup.3 are methyl; Z.sup.12 is
independently hydrogen or methyl; and in formula (2-1), R.sup.c in
R.sup.1 is straight-chain alkyl having 1 to 10 carbons; W.sup.5 is
independently hydrogen or fluorine; and X.sup.4 is a single bond,
--O--, --COO--, --OCO--,--OCO--CH.dbd.CH-- or
--CH.dbd.CH--COO--.
5. The polymerizable liquid crystal composition according to claim
1, wherein a ratio of component (A) is 10 to 97% by weight and a
ratio of component (B) is 3 to 90% by weight, based on the total
weight of component (A) and component (B).
6. The polymerizable liquid crystal composition according to claim
1, wherein a ratio of component (A) is 15 to 85% by weight and a
ratio of component (B) is 15 to 85% by weight, based on the total
weight of component (A) and component (B).
7. The polymerizable liquid crystal composition according to claim
1, further comprising a surfactant.
8. The polymerizable liquid crystal composition according to claim
7, wherein the surfactant is any one of vinyl-based polyalkyl
acrylates, polyalkyl methacrylates, polyalkyl vinyl ethers,
polybutadienes, polyolefins and polyvinyl ethers.
9. The polymerizable liquid crystal composition according to claim
8, further comprising component (F) being a compound selected from
the group of compounds represented by each of formula (6-1) and
formula (6-2): ##STR00082## wherein, in formula (6-1), R.sup.61is a
polymerizable group represented by any one of formulas (R.sup.61-A)
to (R.sup.61--F), hydrogen, chlorine, fluorine, --CN, alkyl having
1 to 10 carbons, alkoxy having 1 to 10 carbons, --CF.sub.3 or
--OCF.sub.3; A.sup.61 is independently 1,4-cyclohexylene,
1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl,
tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl or
bicyclo[2.2.2]octane-1,4-diyl, one or non-adjacent two of
--CH.sub.2-- in 1,4-cyclohexylene may be replaced by --O--, one or
two of --CH.dbd. in 1,4-phenylene may be replaced by --N.dbd., and
arbitrary hydrogen in 1,4-phenylene may be replaced by halogen,
cyano, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons or
alkyl halide having 1 to 5 carbons; X.sup.61 is --CO--,
--COCH.sub.2--, --CO(CH.sub.2).sub.2-- or --COCH.dbd.CH--; x.sup.62
is independently a single bond or alkylene having 1 to 20 carbons,
arbitrary --CH.sub.2-- in the alkylene may be replaced by --O--,
--CO--, --COO--, --OCO--, 13 CH.dbd.CH--, --CF.dbd.CF-- or
--C.ident.C--,and in the groups, arbitrary hydrogen may be replaced
by halogen; Q.sup.61is a single bond or alkylene having 1 to 20
carbons, arbitrary --CH.sub.2-- in the alkylene may be replaced by
--O--, --CO--, --COO--, --OCOO-- or --CH.dbd.CH--, and arbitrary
hydrogen may be replaced by halogen; q61 is an integer from 1 to 5;
Z.sup.61hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl
halide having 1 to 5 carbons; in formulas (R.sup.61-A) to
(R.sup.61--F), Z.sup.62 is independently hydrogen, halogen, alkyl
having 1 to 5 carbons or alkyl halide having 1 to 5 carbons; and in
formula (6-2), Z.sup.62 is independently hydrogen, fluorine, methyl
or trifluoromethyl; W.sup.62 is independently hydrogen, fluorine or
a methoxy; X.sup.63 --O--; X.sup.64 is independently --CH.dbd.CH--
or --CH.sub.2CH.sub.2--; W.sup.63 is hydrogen, methyl,
straight-chain alkyl having 1 to 7 carbons, branched alkyl having 1
to 7 carbons, --COORa where Ra is straight-chain alkyl having 1 to
7 carbons, or --CORb where Rb is straight-chain alkyl having 1 to
15 carbons; and m62 and n62 are independently an integer from 2 to
15.
10. An optical anisotropic film having tilt alignment in an
alignment state of a liquid crystal composition, obtained by curing
the polymerizable liquid crystal composition according to claim 1,
that is coated on a surface treated alignment film.
11. An optical anisotropic film having tilt alignment in an
alignment state of a liquid crystal composition, obtained by curing
the polymerizable liquid crystal composition according to claim 9,
that is coated on a surface treated alignment film.
12. An optical compensation device, comprising the optical
anisotropic film according to claim 10.
13. An optical compensation device, comprising the optical
anisotropic film according to claim 11.
14. An optical device, comprising the optical anisotropic film
according to claim 10 and a polarizing plate.
15. An optical device, comprising the optical anisotropic film
according to claim 11 and a polarizing plate.
16. A liquid crystal display apparatus, comprising the optical
compensation device according to claim 12 on an inner surface or an
outer surface of a liquid crystal cell.
17. A liquid crystal display apparatus, comprising the optical
compensation device according to claim 13 on an inner surface or an
outer surface of a liquid crystal cell.
18. A liquid crystal display apparatus, comprising the optical
device according to claim 14 on an outer surface of a liquid
crystal cell.
19. A liquid crystal display apparatus, comprising the optical
device according to claim 15 on an outer surface of a liquid
crystal cell.
Description
TECHNICAL FIELD
The present invention relates to a polymerizable liquid crystal
composition and an optical anisotropic film obtained therefrom. The
invention also relates to an optical compensation film using the
optical anisotropic film, an optical device and a liquid crystal
display apparatus.
BACKGROUND ART
A polymerizable liquid crystal compound having a liquid crystal
phase yields an optical anisotropic film having a function such as
optical compensation by polymerization because alignment of
polymerizable liquid crystal molecules is immobilized by
poylmerization. Various polymerizable liquid crystal compounds have
been developed in order to utilize such a function of the optical
anisotropic film, but a sufficient function is not satisfied by one
polymerizable liquid crystal compound in some cases. Therefore, an
attempt has been made in which a composition is prepared using
several polymerizable liquid crystal compounds to allow
polymerization of the composition.
In an alignment state of a liquid crystal material, showing a state
of alignment such as homogeneous alignment (horizontal alignment),
tilt alignment (tilted alignment), homeotropic alignment (vertical
alignment) or twist alignment (twisted alignment) is occasionally
described simply as "having homogeneous alignment," "having tilt
alignment," "having homeotropic alignment," "having twist
alignment" or the like.
An optical anisotropic film having the tilt alignment can be
applied to, for example, a viewing angle compensating plate in a
twisted nematic (TN)) mode (see Patent literature No. 1).
In the applications described above, the liquid crystal material
may be occasionally laminated on a support substrate such as a
glass substrate or a plastic substrate. Examples of the material
used as the plastic substrate include a polymer such as triacetyl
cellulose (TAC), polycarbonate, polyethylene terephthalate (PET)
and cycloolefin resins.
Specific examples of the polymerizable liquid crystal composition
in which the liquid crystal material shows the tilt alignment
include a polymerizable liquid crystal composition containing an
acrylate derivative having a 9,9-dialkylfluorene skeleton as a main
component (see Patent literature No. 2), and a polymerizable liquid
crystal composition formed of a monofunctional compound having a
bond in a polymerizable moiety in a center of a mesogen skeleton
and a polymerizable compound having a bisphenol skeleton (see
Patent literature No. 3). Moreover, as a method for controlling
tilt alignment of a liquid crystal material, a proposal has been
made for a method for manufacturing an optical anisotropic film in
which the number of carbon atoms in a spacer group of a
polymerizable liquid crystal compound is controlled (see Patent
literature No. 4).
However, the polymerizable liquid crystal composition described
above is difficult to develop a moderate tilt angle, or when a
polymerizable liquid crystal compound in which the number of carbon
atoms of the spacer group is changed is applied to the composition
for the purpose of controlling the tilt alignment, an amount of
intermediate raw material increases in a manufacturing step,
thereby increasing manufacturing cost in some cases. Therefore, a
desire has been expressed for a polymerizable liquid crystal
composition having structure facilitating development of the tilt
angle of the liquid crystal material in the tilt alignment and
allowing manufacture at low cost.
CITATION LIST
Patent Literature
Patent literature No. 1: JP 2001-55573 A.
Patent literature No. 2: JP 2006-307150 A.
Patent literature No. 3: JP 2008-138142 A.
Patent literature No. 4: JP 2008-134530 A.
SUMMARY OF INVENTION
Technical Problem
An object of the invention is to provide a polymerizable liquid
crystal composition having structure facilitating development of
tilt alignment and facilitating manufacture of a polymerizable
liquid crystal compound. Another object of the invention is to
provide a liquid crystal layer composed of the polymerizable liquid
crystal composition and having controlled tilt alignment, an
optical anisotropic film obtained by polymerizing the polymerizable
liquid crystal composition, and an optical compensation film using
the optical anisotropic composition. A further object of the
invention is to provide an image display apparatus such as a liquid
crystal display apparatus and an organic electroluminescence
display apparatus, including the optical compensation film.
Solution to Problem
The present inventors have found that development of tilt alignment
of a liquid crystal material is facilitated upon utilizing one or
more polymerizable liquid crystal compounds selected from compounds
represented by formulas (1-1), (1-2) and (1-3), and a polymerizable
liquid crystal compound represented by formula (2-1), in
particular, a compound having specified structure represented by
formula (2-1), and thus have completed the invention. The invention
is presented in items 1 to 14 below.
Item 1. A polymerizable liquid crystal composition, containing
component (A) being at least one compound selected from the group
of compounds represented by each of formula (1-1), formula (1-2)
and formula (1-3), and
component (B) being at least one compound selected from the group
of compounds represented by formula (2-1):
##STR00002##
Here, Z.sup.11 is independently hydrogen, fluorine, methyl or
trifluoromethyl; W.sup.1 is independently hydrogen, fluorine or a
methoxy; W.sup.2 and W.sup.3 are independently hydrogen or methyl;
X.sup.1 is independently a single bond or --CH.sub.2CH.sub.2--;
Z.sup.12 is independently hydrogen, fluorine, methyl or
trifluoromethyl; W.sup.4 is hydrogen, methyl, straight-chain alkyl
having 1 to 7 carbons, branched alkyl having 1 to 7 carbons,
alkoxycarbonyl (--COOR.sup.a; R.sup.a is straight-chain alkyl
having 1 to 7 carbons) or alkylcarbonyl (--COR.sup.b; R.sup.b is
straight-chain alkyl having 1 to 15 carbons); X.sup.2 is
independently --O-- or a group represented by formula (a); and m1,
m2, n1 and n2 are independently an integer from 2 to 15.
##STR00003##
Here, Z.sup.21 is hydrogen or methyl; R.sup.1 is an alkyl
ester-containing substituent (--R.sup.d--COOR.sup.c,
--R.sup.d--OCOR.sup.c or --R.sup.d--CH.dbd.CH--COOR.sup.c; R.sup.c
is straight-chain alkyl having 1 to 20 carbons; R.sup.d is a single
bond or straight-chain alkylene having 1 to 10 carbons); W.sup.5 is
independently hydrogen, fluorine or a methoxy; X.sup.3 is
independently a single bond, --COO--, --OCO--, --OCO--CH.dbd.CH--,
--CH.dbd.CH--COO--, --OCO--CH.sub.2CH.sub.2-- or
--CH.sub.2CH.sub.2--COO--; X.sup.4 is a single bond, --O--,
--COO--, --OCO--, formula (a), --OCO--CH.dbd.CH--,
--CH.dbd.CH--COO-- or --OCO--CH.sub.2CH.sub.2--; m3 is an integer
from 2 to 15; and q1 is 0 to 2.
Item 2. The polymerizable liquid crystal composition according to
item 1, wherein,
in formula (1-1) to formula (1-3), Z.sup.11 is independently
hydrogen or methyl; W.sup.1 is independently hydrogen or fluorine;
Z.sup.12 is independently hydrogen or methyl;
and in formula (2-1), R.sup.c in R.sup.1 is straight-chain alkyl
having 1 to 10 carbons; W.sup.5 is independently hydrogen or
fluorine; and X.sup.4 is a single bond, --O--, --COO--, --OCO--,
formula (a), --OCO--CH.dbd.CH-- or --CH.dbd.CH--COO--.
Item 3. The polymerizable liquid crystal composition according to
item 1, wherein,
in formula (1-1) to formula (1-3), Z.sup.11 is independently
hydrogen or methyl; W.sup.1 is independently hydrogen or fluorine;
W.sup.2 is hydrogen and W.sup.3 is methyl; Z.sup.12 is
independently hydrogen or methyl;
and in formula (2-1), R.sup.c in R.sup.l is straight-chain alkyl
having 1 to 10 carbons; W.sup.5 is independently hydrogen or
fluorine; and X.sup.4 is a single bond, --O--, --COO--, --OCO--,
formula (a), --OCO--CH.dbd.CH-- or --CH.dbd.CH--COO--.
Item 4. The polymerizable liquid crystal composition according to
item 1, wherein,
in formula (1-1) to formula (1-3), Z.sup.11 is independently
hydrogen or methyl; W.sup.1 is independently hydrogen or fluorine;
W.sup.2 and W.sup.3 are methyl; Z.sup.12 is independently hydrogen
or methyl;
and in formula (2-1), R.sup.c in R.sup.1 is straight-chain alkyl
having 1 to 10 carbons; W.sup.5 is independently hydrogen or
fluorine; and X.sup.4 is a single bond, --O--, --COO--, --OCO--,
formula (a), --OCO--CH.dbd.CH-- or --CH.dbd.CH--COO--.
Item 5. The polymerizable liquid crystal composition according to
any one of items 1 to 4, wherein a ratio of component (A) is 10 to
97% by weight and a ratio of component (B) is 3 to 90% by weight,
based on the total weight of component (A) and component (B).
Item 6. The polymerizable liquid crystal composition according to
any one of items 1 to 4, wherein a ratio of component (A) is 15 to
85% by weight and a ratio of component (B) is 15 to 85% by weight,
based on the total weight of component (A) and component (B).
Item 7. The polymerizable liquid crystal composition according to
any one of items 1 to 6, further containing a surfactant.
Item 8. The polymerizable liquid crystal composition according to
item 7, wherein the surfactant is one or more selected from
polyalkyl acrylate, polyalkyl methacrylate, polyalkyl vinyl ether,
polybutadiene, polyolefin and polyvinyl ether.
Item 9. The polymerizable liquid crystal composition according to
any one of items 1 to 8, further containing component (F) being a
compound selected from the group of compounds represented by each
of formula (6-1) and formula (6-2).
##STR00004##
In formula (6-1),
R.sup.61 is a polymerizable group represented by any one of
formulas (R.sup.61-A) to (R.sup.61--F), hydrogen, chlorine,
fluorine, cyano, alkyl having 1 to 10 carbons, alkoxy having 1 to
10 carbons, trifluoromethyl or trifluoromethoxy;
A.sup.61 is independently 1,4-cyclohexylene, 1,4-cyclohexenylene,
1,4-phenylene, naphthalene-2,6-diyl,
tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl or
bicyclo[2.2.2]octane-1,4-diyl, one or non-adjacent two of
--CH.sub.2-- in 1,4-cyclohexylene may be replaced by --O--, one or
two of --CH.dbd. in 1,4-phenylene may be replaced by --N.dbd., and
at least one of hydrogen in 1,4-phenylene may be replaced by
halogen, cyano, alkyl having 1 to 5 carbons, alkoxy having 1 to 5
carbons or alkyl halide having 1 to 5 carbons;
X.sup.61 is --CO--, --COCH.sub.2--, --CO(CH.sub.2).sub.2-- or
--COCH.dbd.CH--;
X.sup.62 is independently a single bond or alkylene having 1 to 20
carbons, at least one of --CH.sub.2-- in the alkylene may be
replaced by --O--, --CO--, --COO--, --OCO--, --CH.dbd.CH--,
--CF.dbd.CF-- or --C.ident.C--, and in the groups, at least one of
hydrogen may be replaced by halogen;
Q.sup.61 is a single bond or alkylene having 1 to 20 carbons, at
least one of --CH.sub.2-- in the alkylene may be replaced by --O--,
--CO--, --COO--, --OCO--, --OCOO-- or --CH.dbd.CH--, and in the
groups, at least one of hydrogen may be replaced by halogen;
q61 is an integer from 1 to 5;
Z.sup.61 is hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl
halide having 1 to 5 carbons;
in formulas (R.sup.61-A) to (R.sup.61--F), Z.sup.6a is
independently hydrogen, halogen, alkyl having 1 to 5 carbons or
alkyl halide having 1 to 5 carbons; in formula (6-2),
Z.sup.62 is independently hydrogen, fluorine, methyl or
trifluoromethyl;
W.sup.62 is independently hydrogen, fluorine or a methoxy;
X.sup.63 is independently --O-- or a group represented by formula
(a);
X.sup.64 is independently --CH.dbd.CH-- or
--CH.sub.2CH.sub.2--;
W.sup.63 is hydrogen, methyl, straight-chain alkyl having 1 to 7
carbons, branched alkyl having 1 to 7 carbons, alkoxycarbonyl
(--COOR.sup.a; R.sup.a is straight-chain alkyl having 1 to 7
carbons) or alkylcarbonyl (--COR.sup.b; R.sup.b is straight-chain
alkyl having 1 to 15 carbons); and
m62 and n62 are independently an integer from 2 to 15.
Item 10. An optical anisotropic film having tilt alignment in an
alignment state of a liquid crystal composition, obtained by curing
the polymerizable liquid crystal composition according to items 1
to 9, that is coated on a surface treated alignment film.
Item 11. An optical compensation device, having the optical
anisotropic film according to item 10.
Item 12. An optical device, having the optical anisotropic film
according to item 10 and a polarizing plate.
Item 13. A liquid crystal display apparatus, having the optical
compensation device according to item 11 on an internal plane or
external plane of a liquid crystal cell.
Item 14. A liquid crystal display apparatus, having the optical
device according to item 12 on an external plane of a liquid
crystal cell.
Advantageous Effects of Invention
A polymerizable liquid crystal composition of the invention is
used, thereby facilitating development of tilt alignment and
allowing yielding of an optical anisotropic film having the tilt
alignment of a polymerizable liquid crystal compound at low cost.
The optical anisotropic film of the invention can be applied to
various kinds of optical devices, and the optical devices can be
applied to a display apparatus, in particular, a liquid crystal
display apparatus.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a diagram showing results of measurement of retardation
of an optical anisotropic film showing tilt alignment.
FIG. 2 is a diagram showing results of measurement of retardation
of an optical anisotropic film showing homogeneous alignment.
DESCRIPTION OF EMBODIMENTS
Usage of terms herein is as described below. "Liquid crystal
compound" is a generic term for a compound having a liquid crystal
phase, and a compound having no liquid crystal phase but being
useful as a component of a liquid crystal composition. The liquid
crystal phase includes a nematic phase, a smectic phase and a
cholesteric phase, and in many cases, means the nematic phase.
Polymerizability means capability of a monomer polymerizing by
means of light, heat, a catalyst or the like to give a polymer. A
compound represented by formula (1-1) may be occasionally
represented as compound (1-1). A same rule also applies to any
other compound represented by any other formula. Then,
(meth)acrylate represents one or both of acrylate and methacrylate.
A substituent on a benzene ring in which a bonding hand is
expressed, in a chemical formula, as not bonded with any one of
carbon atoms constituting the benzene ring shows that a bonding
position thereof is arbitrary.
In the invention, a polymerizable liquid crystal composition is
described, for convenience, as a system without containing a
solvent in order to facilitate clear expression of a ratio of the
component. Further, a solution composed of the polymerizable liquid
crystal composition and the solvent is expressed as the solution of
the polymerizable liquid crystal composition. When the system
contains the solvent, the solution of the polymerizable liquid
crystal composition is prepared by dissolving each component of the
polymerizable liquid crystal composition into the solvent.
Alignment in the liquid crystal compound is classified into
"homogeneous (parallel)," "homeotropic (vertical)," "tilt
(tilted)," "twist (twisted)" or the like based on magnitude of a
tilt angle or the like. The tilt angle refers to an angle between
an alignment state of the liquid crystal compound and a support
substrate. "Homogeneous" means a state in which the alignment state
is parallel to the substrate and aligned in one direction. Examples
of the tilt angle in homogeneous alignment include approximately 0
degrees to approximately 5 degrees. "Homeotropic" means a state in
which the alignment state is perpendicular to the substrate.
Examples of the tilt angle in homeotropic alignment include
approximately 85 degrees to approximately 90 degrees. "Tilt" means
a state in which the alignment state further rises from parallel to
perpendicular as the alignment state is further separated from the
substrate. Examples of the tilt angle in tilt alignment include
approximately 5 degrees to approximately 85 degrees. "Twist" means
a state in which the alignment state is parallel to the substrate,
but is twisted stepwise centering on a helical axis. Examples of
the tilt angle in the twist alignment include approximately 0
degrees to approximately 5 degrees.
The composition of the invention contains at least one compound
selected from the group of compounds represented by each of formula
(1-1), formula (1-2) and formula (1-3) as component (A).
##STR00005##
In formula (1-1), formula (1-2) and formula (1-3), Z.sup.11 is
independently hydrogen, fluorine, methyl or trifluoromethyl;
W.sup.1 is independently hydrogen, fluorine or a methoxy; W.sup.2
and W.sup.3 are independently hydrogen or methyl; X.sup.1 is
independently a single bond or --CH.sub.2CH.sub.2--; Z.sup.12 is
independently hydrogen, fluorine, methyl or trifluoromethyl;
W.sup.4 is hydrogen, methyl, straight-chain alkyl having 1 to 7
carbons, branched alkyl having 1 to 7 carbons, alkoxy carbonyl
(--COOR.sup.a; R.sup.a is straight-chain alkyl having 1 to 7
carbons) or alkylcarbonyl (--COR.sup.b; R.sup.b is straight-chain
alkyl having 1 to 15 carbons); X.sup.2 is independently --O-- or a
group represented by formula (a); and m1, m2, n1 and n2 are
independently an integer from 2 to 15, and preferably, an integer
from 2 to 11.
The composition of the invention contains component (B) being at
least one compound represented by formula (2-1)
##STR00006##
In formula (2-1), Z.sup.21 is hydrogen or methyl; R.sup.1 is an
alkyl ester-containing substituent (--R.sup.d--COOR.sup.c,
--R.sup.d--OCOR.sup.c or --R.sup.d--CH.dbd.CH--COOR.sup.c; R.sup.c
is straight-chain alkyl having 1 to 20 carbons (preferably, 1 to
10, further preferably, 1 to 6); R.sup.d is a single bond or
straight-chain alkylene having 1 to 10 carbons (preferably, 1 to 4,
and further preferably, 1 to 2); W.sup.5 is independently hydrogen,
fluorine or a methoxy; X.sup.3 is independently a single bond,
--COO--, --OCO--, --OCO--CH.dbd.CH--, --CH.dbd.CH--COO--,
--OCO--CH.sub.2CH.sub.2-- or --CH.sub.2CH.sub.2--COO--; X.sup.4 is
a single bond, --O--, --COO--, --OCO--, formula (a),
--OCO--CH.dbd.CH--, --CH.dbd.CH--COO-- or
--OCO--CH.sub.2CH.sub.2--; m3 is an integer from 2 to 15, and
preferably, an integer from 2 to 12; and q1 is 0 to 2.
Component (B) has alkyl ester as a terminal group, and thus is
presumed to have strong interaction with a side of a substrate
interface. Thus, development of the tilt alignment is considered to
become easier by adding component (B).
Moreover, structure of component (A) is close to right-left
symmetry and can utilize partial structure used in component (A),
and therefore can be easily manufactured, thereby allowing
obtaining of the polymerizable liquid crystal composition formed
into the tilt alignment at low cost.
The composition of the invention may further contain component (C)
being at least one compound selected from the group of compounds
represented by each of formula (3-1), formula (3-2), formula (3-3),
formula (3-4), formula (3-5) and formula (3-6). The tilt angle can
be further easily increased by adding component (C).
##STR00007##
In formula (3-1), L.sup.1a and L.sup.1b are independently alkyl
having 1 to 4 carbons. R.sup.1a and R.sup.1b are independently
alkylene having 2 to 4 carbons, and preferably, alkylene having 2
carbons, namely, ethylene. Z.sup.31 is independently hydrogen or
methyl, and preferably, hydrogen. Then, k1 and k2 are independently
an integer from 0 to 4, and preferably, 0. Further, m31 and n31 are
independently an integer from 0 to 6, preferably, an integer from 1
to 4, and further preferably, 1.
##STR00008##
In formula (3-2), Z.sup.32 is independently hydrogen or methyl, and
preferably, hydrogen. Then, m32 and n32 are independently an
integer from 1 to 3, and preferably, 1. L.sup.2a and L.sup.2b are
independently alkyl having 1 to 6 carbons, phenyl or fluorine,
preferably, methyl, phenyl or fluorine, and further preferably,
methyl or phenyl. Then, j1 and j2 are independently an integer from
0 to 4, preferably, an integer from 0 to 2, and further preferably,
0.
##STR00009##
In formula (3-3), Z.sup.33 is independently hydrogen or methyl, and
preferably, hydrogen. R.sup.3a and R.sup.3b are independently
hydrogen, methyl or ethyl, and preferably, hydrogen. Furthermore,
m33 and n33 are independently an integer from 0 to 3, and
preferably, an integer from 1 to 3.
##STR00010##
In formula (3-4), Z.sup.34 is hydrogen or methyl, and preferably,
hydrogen. R.sup.4a and R.sup.4b are independently hydrogen or alkyl
having 1 to 6 carbons, and preferably, hydrogen. Then, m34 and n34
are independently an integer from 0 to 10, preferably, an integer
from 0 to 5, and further preferably, an integer from 0 to 2.
##STR00011##
In formula (3-5), Z.sup.35 is independently hydrogen or methyl, and
preferably, hydrogen.
##STR00012##
In formula (3-6), Z.sup.36 is independently hydrogen or methyl, and
preferably, hydrogen. R.sup.5a and R.sup.5b are independently
hydrogen or alkyl having 1 to 6 carbons, and preferably, hydrogen.
L.sup.2a and L.sup.2b are independently alkyl having 1 to 6
carbons, phenyl or fluorine, preferably, methyl, phenyl or
fluorine, and further preferably, methyl or phenyl. Then, m35 and
n35 are independently an integer from 1 to 3, and preferably, 1.
Then, m36 and n36 are independently an integer from 1 to 3, and
preferably, 1. Furthermore, j1 and j2 are independently an integer
from 0 to 4, preferably, an integer from 0 to 2, and further
preferably, 0.
Moreover, the composition of the invention may further contain
component (D) being at least one compound selected from the group
of compounds represented by each of formula (4-1) and formula
(4-2).
##STR00013##
In formula (4-1) and formula (4-2), Z.sup.41 and Z.sup.42 are
independently hydrogen or methyl. Y.sup.1 and Y.sup.2 are
independently a single bond, --(CH.sub.2).sub.2-- or --CH.dbd.CH--.
W.sup.7 and W.sup.8 are independently hydrogen or fluorine. Then,
m5, m6, n5 and n6 are independently an integer from 2 to 15,
preferably, an integer from 2 to 10, further preferably, an integer
from 2 to 8, and still further preferably, an integer from 4 to
6.
Moreover, the composition of the invention may further contain
component (E) being at least one compound selected from the group
of compounds represented by formula (5-1).
##STR00014##
In formula (5-1), Z.sup.51 is hydrogen or methyl; R.sup.51 is
cyano, trifluoromethoxy, alkyl having 1 to 20 carbons or alkoxy
having 1 to 20 carbons; ring E represents a benzene ring or a
cyclohexane ring; W.sup.9 is independently hydrogen, fluorine or a
methoxy; X.sup.52 is independently a single bond, --COO--, --OCO--,
--OCO--CH.dbd.CH--, --CH.dbd.CH--COO--, --OCO--CH.sub.2CH.sub.2--
or --CH.sub.2CH.sub.2--COO--; X.sup.51 is a single bond, --O--,
--COO--, --OCO--, formula (a), --OCO--CH.dbd.CH--,
--CH.dbd.CH--COO-- or --OCO--CH.sub.2CH.sub.2--; m7 is an integer
from 2 to 15, and preferably, an integer from 2 to 12; and q7 is 0
to 2.
Moreover, the composition of the invention may further contain
component (F) being at least one compound selected from the group
of compounds represented by formula (6-1) and formula (6-2).
##STR00015##
In formula (6-1),
R.sup.61 is a polymerizable group represented by any one of
formulas (R.sup.61-A) to (R.sup.61--F), hydrogen, chlorine,
fluorine, cyano, alkyl having 1 to 10 carbons, alkoxy having 1 to
10 carbons, trifluoromethyl or trifluoromethoxy;
A.sup.61 is independently 1,4-cyclohexylene, 1,4-cyclohexenylene,
1,4-phenylene, naphthalene-2,6-diyl,
tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl or
bicyclo[2.2.2]octane-1,4-diyl, one or non-adjacent two of
--CH.sub.2-- in 1,4-cyclohexylene may be replaced by --O--, one or
two of --CH.dbd. in 1,4-phenylene may be replaced by --N.dbd., and
at least one of hydrogen in 1,4-phenylene may be replaced by
halogen, cyano, alkyl having 1 to 5 carbons, alkoxy having 1 to 5
carbons or alkyl halide having 1 to 5 carbons;
X.sup.61 is --CO--, --COCH.sub.2--, --CO(CH.sub.2).sub.2-- or
--COCH.dbd.CH--;
X.sup.62 is independently a single bond or alkylene having 1 to 20
carbons, at least one of --CH.sub.2-- in the alkylene may be
replaced by --O--, --CO--, --COO--, --OCO--, --CH.dbd.CH--,
--CF.dbd.CF-- or --C.ident.C--, and in the groups, at least one of
hydrogen may be replaced by halogen;
Q.sup.61 is a single bond or alkylene having 1 to 20 carbons, at
least one of --CH.sub.2-- in the alkylene may be replaced by --O--,
--CO--, --COO--, --OCO--, --OCOO-- or --CH.dbd.CH--, and in the
groups, at least one of hydrogen may be replaced by halogen;
q61 is an integer from 1 to 5; and
Z.sup.61 is hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl
halide having 1 to 5 carbons.
In formulas (R.sup.61-A) to (R.sup.61--F), Z.sup.6a is
independently hydrogen, halogen, alkyl having 1 to 5 carbons or
alkyl halide having 1 to 5 carbons.
In addition, in the invention, halogen refers to Group 17 elements,
and specifically, fluorine, chlorine, bromine or iodine, and
preferably, fluorine, chlorine or bromine.
In formula (6-2),
Z.sup.62 is independently hydrogen, fluorine, methyl or
trifluoromethyl;
W.sup.62 is independently hydrogen, fluorine or a methoxy;
X.sup.63 is independently --O-- or a group represented by formula
(a);
X.sup.64 is independently --CH.dbd.CH-- or
--CH.sub.2CH.sub.2--;
W.sup.63 is hydrogen, methyl, straight-chain alkyl having 1 to 7
carbons, branched alkyl having 1 to 7 carbons, alkoxycarbonyl
(--COOR.sup.a; R.sup.a is straight-chain alkyl having 1 to 7
carbons) or alkylcarbonyl (--COR.sup.b; R.sup.b is straight-chain
alkyl having 1 to 15 carbons); and
m62 and n62 are independently an integer from 2 to 15.
The polymerizable liquid crystal composition of the invention has
the nematic phase at room temperature, and is subjected to the tilt
alignment on a plastic substrate subjected to photo-alignment
treatment or rubbing alignment treatment, or on an alignment film
such as a polyimide film subjected to photo-alignment treatment or
rubbing alignment treatment. If the composition of the invention
contains a monofunctional component represented by formula (2-1)
(namely, component (B)), the composition has stronger trend of the
tilt alignment on the alignment film subjected to alignment
treatment. Moreover, the composition of the invention is easily
subjected to the tilt alignment also when the composition contains
a bifunctional component (namely, component (A)) represented by
formulas (1-1) to (1-3) in which a fluorene ring or benzene ring
being center structure of a mesogen skeleton is asymmetrical.
The compounds used for the composition of the invention will be
described.
The compounds represented by formula (1-1), formula (1-2) and
formula (1-3) have two polymerizable groups. A polymer of the
polymerizable liquid crystal compound can be formed into
three-dimensional structure, and therefore the compound give a
harder polymer in comparison with a compound having one
polymerizable group. The compounds represented by formula (1-1),
formula (1-2) and formula (1-3) exhibit the liquid crystal phase
over a wide temperature range. Moreover, the compounds is easily
subjected to the homogeneous alignment with regard to a trend of
tilt angle development, and tends to be subjected to the tilt
alignment when the fluorene ring or benzene ring being the center
structure of the mesogen skeleton is asymmetrical, although a tilt
angle depends on a state of an additive or a support substrate.
The compound represented by formula (2-1) has one polymerizable
group. The compound represented by formula (2-1) has properties of
increasing the tilt angle or properties of decreasing a melting
point.
The compounds represented by formula (3-1) to formula (3-6) include
no liquid crystal compounds. The compounds represented by formula
(3-1) to formula (3-6) have fluorene structure and phenoxide
structure in one molecule. Moreover, the compounds represented by
formula (3-1) to formula (3-6) are effective in homeotropically
aligning the liquid crystal compound. In the explanation below,
formula (3) may be occasionally used as a generic term for the
compounds represented by formula (3-1) to formula (3-6).
The compounds represented by formula (4-1) and formula (4-2) have a
bisphenol skeleton and two polymerizable groups. A polymer of the
polymerizable compounds can be formed into three-dimensional
structure, and therefore the compounds give a harder polymer in
comparison with the compound having one polymerizable group. The
compounds represented by formula (4-1) and formula (4-2) do not
always need to exhibit liquid crystallinity. Moreover, the
compounds represented by formula (4-1) and formula (4-2) have
property of decreasing the melting point of the polymerizable
liquid crystal composition. If the compounds represented by formula
(4-1) and formula (4-2) are simultaneously used with other
polymerizable liquid crystal compounds, the resulting mixture tends
to be easily subjected to the homeotropic alignment, although a
tilt angle depends on the conditions for the support substrate, the
additive or the like.
The compounds represented by formula (5-1), formula (6-1) and
formula (6-2) may be simultaneously used in order to control
birefringence (.DELTA.n) of the polymerizable liquid crystal
composition. The compounds represented by formula (5-1) and formula
(6-1) allow control of .DELTA.n to a low level, and the compound
represented by formula (6-2) allows control of .DELTA.n to a high
level, when a cinnamate bond is selected.
The composition of the invention may contain any other
polymerizable compound (hereinafter, also referred to as "any other
polymerizable compound") different from the compounds represented
by formulas (1-1) to (1-3), formula (2-1), formula (3-1) to formula
(3-6), formula (4-1), formula (4-2), formula (5-1), formula (6-1)
and formula (6-2). The composition may further contain an additive
such as a surfactant for forming a paint film having a uniform
thickness, and for suppressing an alignment defect being a
phenomenon in which directions of tilt angle rise of the
polymerizable liquid crystal are different. The composition may
also contain an additive such as a polymerization initiator and
photosensitizer suitable for a polymerization reaction.
The composition may also contain an additive such as an ultraviolet
light absorber, an antioxidant, a radical scavenger and a light
stabilizer in order to improve polymer characteristics. The
composition may also contain an organic solvent allowing sufficient
dissolution of the polymerizable liquid crystal composition without
damaging the support substrate. The organic solvent is useful for
forming a paint film having a uniform thickness. Moreover, the
composition may also contain a dichroic dye in order to provide the
polymer (liquid crystal film) with polarization
characteristics.
A ratio of each component in the composition of the invention will
be described.
A preferred ratio of component (A) is approximately 10 to
approximately 97% by weight based on the total weight of component
(A) and component (B). A further preferred ratio is approximately
15 to approximately 85% by weight based thereon.
A preferred ratio of component (B) is approximately 3 to
approximately 90% by weight based on the total weight of component
(A) and component (B). A further preferred ratio is approximately
15 to approximately 85% by weight based thereon.
A preferred ratio when using component (C) is approximately 0.01 to
approximately 0.20 in terms of a weight ratio based on the total
weight of component (A) and component (B). A further preferred
weight ratio is approximately 0.03 to approximately 0.15 based
thereon.
A preferred ratio when using component (D) is approximately 0.01 to
approximately 0.25 in terms of the weight ratio based on the total
weight of component (A) and component (B). A further preferred
ratio is approximately 0.03 to approximately 0.15 based
thereon.
A preferred ratio when using component (E) is approximately 0.01 to
approximately 1.00 in terms of the weight ration based on the total
weight of component (A) and component (B). A further preferred
ratio is approximately 0.03 to approximately 0.50 based thereon. In
addition, when using a compound having a cyano group in a terminal
group as component (E), a preferred ratio is approximately 0.03 to
approximately 1.00 in terms of the weight ratio based on the total
weight of component (A) and component (B) from a viewpoint of
facilitating development of the tilt alignment.
A preferred ratio when using component (F) is approximately 0.01 to
approximately 1.00 in terms of the weight ratio based on the total
weight of component (A) and component (B). A further preferred
ratio is approximately 0.03 to approximately 0.50 based
thereon.
A preferred amount of addition when using any other polymerizable
compound is approximately 0.01 to approximately 0.40, and a further
preferred ratio is approximately 0.03 to approximately 0.25, in
terms of the weight ratio based on the total weight of component
(A) and component (B). When the additive such as the surfactant and
the polymerization initiator is used, an amount used may be minimum
amount for attaining the object.
A combination of each component in the composition of the invention
will be described.
A preferred combination includes a combination of component (A) and
component (B).
When controlling the tilt angle, a combination of component (A),
component (B) and component (C); a combination of component (A),
component (B) and component (D); and a combination of component
(A), component (B), component (C) and component (D) are
preferred.
With regard to each combination, component (E), component (F) and
any other polymerizable compound may be further combined.
Next, methods for synthesizing the compounds will be described. The
compounds used in the invention can be synthesized by combining
synthesis methods in organic chemistry described in Houben-Wyle,
Methoden der Organischen Chemie (Georg-Thieme Verlag, Stuttgart),
Organic Reactions (John Wily & Sons, Inc.), Organic Syntheses
(John Wily & Sons, Inc.), Comprehensive Organic Synthesis
(Pergamon Press), New Experimental Chemistry Course (Shin Jikken
Kagaku Koza in Japanese) (Maruzen Co., Ltd.) or the like.
A method for synthesizing the compound represented by formula (1-1)
is described in JP 2003-238491 A and JP 2006-307150 A. A method for
synthesizing the compound represented by formula (1-2) is described
in Makromol. Chem., 190, 3201-3215 (1998), WO 97/00600 A or the
like. As for a method for synthesizing the compound represented by
formula (1-3), a method described in U.S. Pat. No. 5,770,107 B or
JP 2012-177087 A can be used as a reference.
In a method for introducing .alpha.-fluoroacryloyloxy
(CH.sub.2.dbd.CF--COO--), .alpha.-fluoroacrylic acid or
.alpha.-fluoroacrylic acid chloride can also be used, but a method
for acting .alpha.-fluoroacrylic acid fluoride
(CH.sub.2.dbd.CFCOOF) thereon is useful. A method for synthesizing
.alpha.-fluoroacrylic acid fluoride is described in J. Org. Chem.,
1989, 54, 5640, JP S60-158137 A, JP S61-85345 A or the like, and
synthesis can be made in accordance with the methods. The compounds
are used as a starting material, thereby allowing synthesis of the
compounds represented by formula (1-1) and formula (1-2).
As methods for synthesizing the compounds represented by formula
(2-1) and formula (5-1), synthesis can be made by the methods
described in Macromolecules, 26, 6132-6134 (1993), Makromol. Chem.,
183, 2311-2321 (1982), DE 19504224 B, WO 1997/00600 A, U.S. Pat.
No. 4,952,334 B, U.S. Pat. No. 4,842,754 B or the like.
A method for synthesizing the compound represented by formula (3)
is described in the literature below. Formula (3-1): WO 2005/33061
A. Formula (3-2) to formula (3-4): JP 2005-338550 A. Formula (3-4):
JP 2002-293762 A. Formula (3-5): JP 2005-272485 A. Precursor
(epoxyacrylate precursor) of the compound of formula (3-6): JP
2002-348357 A.
A method for synthesizing the compounds represented by formula
(4-1) and formula (4-2) is described in JP 2007-16213 A.
A method for synthesizing the compounds represented by formula
(6-1) is described in JP 2011-246365 A. A method for synthesizing
the compounds represented by formula (6-2) is described in U.S.
Pat. No. 5,770,107 B.
Next, examples of component compounds are shown. Preferred examples
of the compound represented by formula (1-1) are shown below.
##STR00016##
In formulas (1-1-A) to (1-1-D), Z.sup.11 is independently hydrogen,
fluorine, methyl or trifluoromethyl, and m1 and n1 are each
independently an integer from 2 to 15, and preferably, an integer
from 2 to 11.
Preferred examples of the compound represented by formula (1-2) are
shown below.
##STR00017## ##STR00018## ##STR00019##
In formulas (1-2-A) to (1-2-L), Z.sup.12 is independently hydrogen,
fluorine, methyl or trifluoromethyl, and m2 and n2 are each
independently an integer from 2 to 15, and preferably, an integer
from 2 to 11.
Preferred examples of the compound represented by formula (1-3) are
shown below.
##STR00020##
In formulas (1-3-A) to (1-3-B), Z.sup.11 is independently hydrogen,
fluorine, methyl or trifluoromethyl, W.sup.1 is independently
hydrogen or fluorine, and m1 and n1 are each independently an
integer from 2 to 15, and preferably, an integer from 2 to 11. The
compounds represented by formulas (1-3-A) to (1-3-B) are preferably
a trans isomer, and both of --CH.dbd.CH-- further preferably take a
trans form.
Preferred examples of the compound represented by formula (2-1) are
shown below.
##STR00021##
In formulas (2-1-A) to formula (2-1-I), Z.sup.21 is hydrogen or
methyl, W.sup.5 is hydrogen or fluorine and R.sup.1 and m.sup.3 are
defined in a manner similar as described above.
In formula (2-1-D) and formula (2-1-E), a trans isomer is further
preferred.
Preferred examples of the compounds represented by formula (3-1) to
formula (3-6) are shown below.
##STR00022## wherein, Z.sup.31 is independently hydrogen or methyl,
R.sup.1a and R.sup.1b are independently alkylene having 2 to 4
carbons, and m31 and n31 are independently an integer from 0 to
6.
##STR00023## wherein, Z.sup.32 is independently hydrogen or methyl,
and m32 and n32 are independently an integer from 1 to 3.
##STR00024## wherein, Z.sup.33 is independently hydrogen or methyl,
and m33 and n33 are independently an integer from 0 to 3.
##STR00025## wherein, Z.sup.34 is hydrogen or methyl, and m34 and
n34 are independently an integer from 0 to 10.
##STR00026## wherein, Z.sup.35 is independently hydrogen or
methyl.
##STR00027## wherein, Z.sup.36 is independently hydrogen or methyl,
m35 and n35 are independently an integer from 1 to 3, and m36 and
n36 are independently an integer from 1 to 3.
Preferred examples of the compounds represented by formula (4-1)
and formula (4-2) are shown below.
##STR00028##
In formula (4-1-A) to formula (4-1-C), Z.sup.41 is independently
hydrogen or methyl, W.sup.7 is independently hydrogen or fluorine,
and m5 and n5 are independently an integer from 2 to 15. In formula
(4-2-A) to formula (4-2-C), Z.sup.42 is independently hydrogen or
methyl, W.sup.8 is independently hydrogen or fluorine, and m6 and
n6 are independently an integer from 2 to 15. In formula (4-1-B)
and formula (4-2-B), a trans isomer is preferred, and both of
--CH.dbd.CH-- further preferably take a trans form.
Preferred examples of the compound represented by formula (5-1) are
shown below.
##STR00029## ##STR00030##
In formula (5-1-A) to formula (5-1-Q), Z.sup.51 is hydrogen or
methyl, W.sup.9 is hydrogen or fluorine, R.sup.51 is alkyl having 1
to 20 carbons, alkoxy having 1 to 20 carbons or trifluoromethoxy,
m7 is an integer from 2 to 15, and preferably, an integer from 2 to
12.
In formula (5-1-G) to formula (5-1-J), a trans isomer is further
preferred.
Preferred examples of the compound represented by formula (6-1) are
shown below.
##STR00031## ##STR00032## ##STR00033##
In formula (6-1-1) to formula (6-1-19), R is hydrogen, alkyl having
1 to 10 carbons, alkoxy having 1 to 10 carbons, trifluoromethyl or
trifluoromethoxy.
Moreover, in formula (6-1-9), formula (6-1-16) and formula
(6-1-18), a trans isomer is further preferred.
##STR00034## ##STR00035## ##STR00036## ##STR00037##
In formula (6-1-28), formula (6-1-32) and formula (6-1-37), a trans
isomer is further preferred, the compound represented by formula
(6-1-33) is preferably a trans isomer, and both of --CH.dbd.CH--
further preferably take a trans form.
Preferred examples of the compound represented by formula (6-2) are
shown below.
##STR00038##
In formula (6-2-A) to formula (6-2-F),
Z.sup.62 is independently hydrogen, fluorine, methyl or
trifluoromethyl,
W.sup.63 is hydrogen, methyl, straight-chain alkyl having 1 to 7
carbons or branched alkyl having 1 to 7 carbons,
R.sup.a is straight-chain alkyl having 1 to 7 carbons,
R.sup.b is straight-chain alkyl having 1 to 15 carbons, and
m62 and n62 are independently an integer from 2 to 15.
In formula (6-2-A), formula (6-2-C) and formula (6-2-E), a trans
isomer is preferred, and both of --CH.dbd.CH-- further preferably
take a trans form.
Furthermore, specific preferred examples of the compounds
represented by formula (1-1) to formula (1-3), formula (2-1),
formula (3-1) to formula (3-6), formula (4-1), formula (4-2),
formula (5-1), formula (6-1) and formula (6-2) are shown below.
##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043##
##STR00044##
In formula (1-3-A-1) to formula (1-3-A-4), and formula (1-3-B-1) to
formula (1-3-B-4), a trans isomer is preferred, and both of
--CH.dbd.CH-- further preferably take a trans form.
##STR00045## ##STR00046##
In formula (2-1-12) to formula (2-1-15), a trans isomer is further
preferred.
##STR00047##
Specific examples of the compound represented by formula (3) are
shown below.
##STR00048##
In the formulas, n is each independently an integer from 1 to
4.
##STR00049##
In the formulas, n is each independently an integer from 1 to
3.
##STR00050##
In the formulas, n is each independently an integer from 1 to
3.
##STR00051##
In the formulas, n is each independently an integer from 0 to
2.
##STR00052##
Specific examples of commercial items including the compounds
represented by formula (3-1-1), formula (3-2-1), formula (3-3-1) or
formula (3-6-1) include OGSOL (registered trademark) EA-0250T,
OGSOL EA-0500, OGSOL EA-1000, CA-0400, CA-0450T, ONF-1, BPEFA,
GA-1000 or the like made by Osaka Gas Chemicals Co., Ltd. The
commercial items may also be used.
Specific examples of the compound represented by formula (4) are
shown below.
##STR00053##
In formula (4-1-2) to formula (4-1-4), a trans isomer is preferred,
and both of --CH.dbd.CH-- further preferably take a trans form.
##STR00054## ##STR00055##
In formula (4-2-5) to formula (4-2-7), a trans isomer is preferred,
and both of --CH.dbd.CH-- further preferably take a trans form.
##STR00056##
Preferred examples of the compound represented by formula (5-1) are
shown below.
##STR00057## ##STR00058##
In formula (5-1-16) to formula (5-1-23), a trans isomer is further
preferred.
##STR00059## ##STR00060## ##STR00061## ##STR00062##
In formula (5-1-65) and formula (5-1-66), a trans isomer is further
preferred.
##STR00063## ##STR00064##
In formula (6-1-16-1), a trans isomer is further preferred.
##STR00065##
In formula (6-2-A-1) to formula (6-2-A-4), a trans isomer is
preferred, and both of --CH.dbd.CH-- further preferably take a
trans form.
##STR00066## ##STR00067##
In formula (6-2-C-1) to formula (6-2-C-3), a trans isomer is
preferred, and both of --CH.dbd.CH-- further preferably take a
trans form.
##STR00068## ##STR00069##
In formula (6-2-E-1) to formula (6-2-E-3), a trans isomer is
preferred, and both of --CH.dbd.CH-- further preferably take a
trans form.
Next, specific examples of any other polymerizable compound, the
additive and the organic solvent are described, and the compounds
may include a commercial item. Specific examples of any other
polymerizable compound include a compound having one polymerizable
group, a compound having two polymerizable groups, a compound
having three or more polymerizable groups, a non-liquid crystalline
polymerizable compound having a functional group including a
hydroxyl and having an acryloyl or a methacryloyl in one compound,
a polymerizable compound having a carboxyl and a polymerizable
compound having a phosphate.
Specific examples of the compound having one polymerizable group
but having no functional group including the hydroxyl include
styrene, nucleus-substituted styrene, acrylonitrile, vinyl
chloride, vinylidene chloride, vinylpyridine, N-vinyl pyrrolidone,
vinylsulfonic acid, fatty acid vinyl (vinyl acetate),
.alpha.,.beta.-ethylenic unsaturated carboxylic acid (acrylic acid,
methacrylic acid, maleic acid, fumaric acid, itaconic acid), alkyl
ester of (meth)acrylic acid (number of carbons in alkyl: 1 to 18),
hydroxyalkyl ester of (meth)acrylic acid (number of carbons in
hydroxyalkyl: 1 to 18), aminoalkyl ester of (meth)acrylic acid
(number of carbons in aminoalkyl: 1 to 18), ether oxygen-containing
alkylester of (meth)acrylic acid (number of carbons in ether
oxygen-containing alkyl: 3 to 18, such as methoxyethyl ester,
ethoxyethyl ester, methoxypropyl ester, methylcarbyl ester,
ethylcarbyl ester and butylcarbyl ester), N-vinylacetamide, vinyl
p-t-butylbenzoate, vinyl N,N-dimethylaminobenzoate, vinyl benzoate,
vinyl pivalate, vinyl 2,2-dimethylaminobenzoate, vinyl
2,2-dimethylpentanoate, vinyl 2-methyl-2-methyl-2-butanoate, vinyl
propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutanoate,
dicyclopentaniloxylethyl (meth)acrylate, isobornyloxylethyl
(meth)acrylate, isobornyl (meth)acrylate, adamanthyl
(meth)acrylate, dimethyl adamanthyl (meth)acrylate,
dicyclopentanyl(meth)acrylate, dicyclopentenyl (meth)acrylate,
mono(meth)acrylic acid ester of polyethylene glycol (number of
repeating units (degree of polymerization): 2 to 20) a terminal
group of which is capped by alkyl having 1 to 6 carbons, mono
(meth)acrylic ester of polypropylene glycol (number of repeating
units (degree of polymerization): 2 to 20) a terminal group of
which is capped by alkyl having 1 to 6 carbons, and mono
(meth)acrylic ester of polyalkylene glycol such as a copolymer
(degrees of polymerization: 2 to 20) of ethylene oxide and
propylene oxide a terminal group of which is capped by alkyl having
1 to 6 carbons.
Specific examples of the compound having two polymerizable groups
but having no functional group including the hydroxyl include
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate,
1,9-nonanediol diacrylate, neopentylglycol diacrylate,
dimethyloltricyclodecane diacrylate, triethyleneglycol diacrylate,
dipropyleneglycol diacrylate, tripropyleneglycol diacrylate,
tetraethyleneglycol diacrylate, bisphenol A EO-added diacrylate,
bisphenol A glycidyl diacrylate (Viscoat V#700), polyethylene
glycol diacrylate and a methacrylate compound of the compound
thereof. The compounds are suitable for further improving
film-formation capability of a polymer.
Specific examples of the compound having three or more
polymerizable groups but having no functional group including the
hydroxyl include trimethylolpropane tri(meth)acrylate, trimethylol
EO-added tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate,
tris(meth)(acryloyloxyethyl)isocyanurate, alkyl-modified
dipentaerythritol tri(meth)acrylate, EO-modified trimethylolpropane
tri (meth)acrylate, PO-modified trimethylolpropane tri
(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkyl-modified
dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane
tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate,
alkyl-modified dipentaerythritol penta(meth)acrylate, Viscoat V#802
(number of functional groups=8) and Viscoat V#1000 (number of
functional groups=14 on average). "Viscoat" is a trade name of
products from Osaka Organic Chemical Industry Ltd. A compound
having 16 or more functional groups can be obtained by using
Boltorn H20 (16 functional groups), Boltorn H30 (32 functional
groups) and Boltorn H40 (64 functional groups) sold by Perstorp
Specialty Chemicals as a raw material and acrylating the raw
material.
The non-liquid crystalline polymerizable compound having the
functional group including the hydroxyl and having the acryloyl or
methacryloyl in one compound may include a commercial item.
Preferred examples include butanediol monoacrylate, a reaction
product between butyl glycidyl ether and (meth)acrylic acid
(Denacol DA-151 (registered trademark), made by Nagase & Co.,
Ltd.), 3-chloro-2-hydroxypropyl methacrylate, glycerol methacrylate
(Blemmer (registered trade mark) GLM, made by NOF Corporation),
glycerol acrylate, glycerol dimethacrylate (Blemmer GMR series,
made by NOF Corporation), glycerol triacrylate (EX-314, made by
Nagase ChemteX Corporation), 2-hydroxyethyl acrylate (BHEA, made by
Nippon Shokubai Co., Ltd.), 2-hydroxyethyl methacrylate (HEMA, made
by Nippon Shokubai Co., Ltd.), 2-hydroxypropyl acrylate (HPA, made
by NIPPON SHOKUBAI CO., LTD.), 2-hydroxypropyl methacrylate (HPMA,
made by Nippon Shokubai Co., Ltd.), caprolactone-modified
2-hydroxyethyl acrylate, caprolactone-modified 2-hydroxyethyl
methacrylate, phenoxyhydroxypropyl acrylate (M-600A, made by
Kyoeisha Chemical Co., Ltd.), 2-hydroxy-3-acryloyloxypropyl
methacrylate (G-201P, made by Kyoeisha Chemical Co., Ltd.), Kayarad
(registered trademark) R-167, made by Nippon Kayaku Co., Ltd.,
triglycerol diacrylate (Epoxy Ester 80MFA, made by Kyoeisha
Chemical Co., Ltd.), pentaerythritol tri(meth)acrylate,
dipentaerythritolmonohydroxy penta(meth)acrylate,
2-acryloyloxyethyl succinate, 2-acryloyloxyethyl
hexahydrophthalate, 2-acryloyloxyethyl phthalate,
2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxyethyl
acid phosphate, L-methacryloxyethyl acid phosphate,
2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl
hexahydrophthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate,
4-(2-acryloyloxyeth-1-yloxy)benzoic acid,
4-(3-acryloyloxy-n-prop-1-yloxy)benzoic acid,
4-(2-methacryloyloxyeth-1-yloxy)benzoic acid,
4-(4-acryloyloxy-n-but-1-yloxy)benzoic acid,
4-(6-acryloyloxy-n-hex-1-yloxy)benzoic acid,
4-(6-acryloyloxy-n-hex-1-yloxy)-2-methyl benzoic acid,
4-(6-methacryloyloxy-n-hex-1-yloxy)benzoic acid,
4-(10-acryloyloxy-n-dec-1-yloxy)benzoic acid, 2-acryloyloxyethyl
acid phosphate and 2-methacryloiloxy-ethyl acid phosphate.
Specific examples of monomethacrylic acid ester of polyethylene
glycol having a degree of polymerization from 2 to 20, as
exemplified by formula (7-1) described below, include Blemmer PE-90
(n=2), PE-200 (n=4.5) and PE-350 (n=8), as made by NOF Corporation.
Here, the number of repeating units of a polyethylene glycol chain
(degree of polymerization) is further preferably 2 to 10, in which
n represents the number of average constitutional units.
##STR00070##
Specific examples of monoacrylic ester of polyethylene glycol
having a degree of polymerization from 2 to 20 include, as
exemplified by formula (7-2) described below, Blemmer AE-90 (n=2),
AE-200 (n=4.5) and AE-400 (n=10), as made by NOF Corporation. Here,
the number of repeating units of a polyethylene glycol chain
(degree of polymerization) is further preferably 2 to 10.
##STR00071##
Specific examples of monomethacrylic acid ester of polypropylene
glycol having a degree of polymerization from 2 to 20 include, as
exemplified by formula (7-3) described below, Blemmer PP-1000 (n=4
to 6), PP-500 (n=9) and PP-800 (n=13), as made by NOF Corporation.
Here, the number of repeating units of a polyethylene glycol chain
(degree of polymerization) is further preferably 3 to 13.
##STR00072##
Specific examples of monoacrylic ester of polypropylene glycol
having a degree of polymerization from 2 to 20 include, as
exemplified by formula (7-4) described below, Blemmer AP-150 (n=3),
AP-400 (n=6), AP-550 (n=9) and AP-800 (n=13), as made by NOF
Corporation. Here, the number of repeating units of a polyethylene
glycol chain (degree of polymerization) is further preferably 3 to
13.
##STR00073##
Specific examples of poly(ethylene glycol-propylene glycol)
monomethacrylic acid ester include, as exemplified by formula (7-5)
described below, Blemmer 50PEP-300, made by NOF Corporation. Here,
ethylene or propylene that means R is randomly copolymerized. The
mean number (m) of constitutional units of ethyleneoxy and
propyleneoxy is approximately 2.5 and approximately 3.5,
respectively. Further, m described below also represents the mean
number of constitutional units of each alkylene.
##STR00074##
Specific examples of poly'ethylene glycol-propylene glycol)
monomethacrylic acid ester include, as exemplified by formula (7-6)
described below, Blemmer 70PEP-350 B (m=5, n=2), made by NOF
Corporation.
##STR00075##
Specific examples of polyethylene glycol-polypropylene glycol
monoacrylic acid ester include Blemmer AEP series.
Specific examples of poly(ethylene glycol-tetramethylene glycol)
monomethacrylic acid ester include, as exemplified by formula (7-7)
described below, Blemmer 55PET-400, 30PET-800 and 55PET-800, made
by NOF Corporation. Here, the number of repeating units of a
poly(ethylene glycol-tetramethylene glycol) chain is further
preferably 2 to 10. In the formula, ethylene or butylene that means
R is randomly copolymerized. The mean number (m) of constitutional
units of ethyleneoxy and butyleneoxy is 5 and 2 in 55PET-400, 6 and
10 in 30PET-800, and 10 and 5 in 55PET-800, respectively.
##STR00076##
Specific examples of poly(ethylene glycol-tetramethylene glycol)
monoacrylic acid ester include Blemmer AET series, made by NOF
Corporation.
Specific examples of poly (propylene glycol-tetramethylene glycol)
monomethacrylic acid ester include, as exemplified by formula (7-8)
described below, Blemmer 30PPT-800, 50PPT-800 and 70PPT-800, made
by NOF Corporation. Here, the number of repeating units of a poly
(propylene glycol-tetramethylene glycol) chain is further
preferably 3 to 10. In the formula, propyleneoxy or butyleneoxy
that means R is randomly copolymerized. The mean number (m) of
constitutional units of propylene and butylene is 4 and 8 in
30PPT-800, 7 and 6 in 50PPT-800 and 10 and 3 in 70PPT-800,
respectively.
##STR00077##
Specific examples of poly (propylene glycol-tetramethylene glycol)
monoacrylic acid ester include Blemmer APT series, made by NOF
Corporation.
Specific examples of propylene glycol-polybutylene glycol
mono((meth)acrylic ester) include, as exemplified by formula (7-9)
described below, Blemmer 10PPB-500B (n=6), and as exemplified by
formula (7-10) described below, 10APB-500B (n=6), as made by NOF
Corporation. Here, the number of repeating units of a propylene
glycol-polybutylene glycol chain is further preferably 6.
##STR00078##
Preferred examples of the polymerizable compound having the
carboxyl are described below, and may include a commercial
item.
Preferred examples include 2-methacryloyloxyethyl succinate (Light
Ester HO-MS (N), made by Kyoeisha Chemical Co.), Ltd.),
2-methacryloyloxyethyl hexahydrophthalate (Light Ester HO-HH (N),
made by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl succinate
(Light Ester HOA-MS (N), made by Kyoeisha Chemical Co., Ltd.),
2-acryloyloxyethyl hexahydrophthalate (Light Acrylate HOA-HH (N),
made by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl phthalate
(Light Acrylate HOA-MPL (N), made by Kyoeisha Chemical Co., Ltd.),
2-acryloyloxyethyl-2-hydroxyethyl phthalate (Light Acrylate HOA-MPE
(N), made by Kyoeisha Chemical Co., Ltd.),
4-(2-acryloyloxyeth-1-yloxy) benzoic acid (ST01630, made by Synthon
Chemicals GmbH & Co. KG), 4-(3-acryloyloxy-n-prop-1-yloxy)
benzoic acid (ST02453, made by Synthon Chemicals GmbH & Co.
KG), 4-(2-methacryloyloxyeth-1-yloxy) benzoic acid (ST01889, made
by Synthon Chemicals GmbH & Co. KG),
4-(4-acryloyloxy-n-but-1-yloxy) benzoic acid (ST01680, made by
Synthon Chemicals GmbH & Co. KG),
4-(6-acryloyloxy-n-hex-1-yloxy) benzoic acid (ST00902, made by
Synthon Chemicals GmbH & Co. KG),
4-(6-acryloyloxy-n-hex-1-yloxy)-2-methylbenzoic acid (ST03606, made
by Synthon Chemicals GmbH & Co. KG),
4-(6-methacryloyloxy-n-hex-1-yloxy) benzoic acid (ST01618, made by
Synthon Chemicals GmbH & Co. KG) and
4-(10-acryloyloxy-n-dec-1-yloxy) benzoic acid (ST03604, made by
Synthon Chemicals GmbH & Co. KG).
Preferred examples of the polymerizabie compound having the
phosphate are described below, and may include a commercial
item.
Specific examples include 2-acryloyloxyethyl acid phosphate (Light
Acrylate P-1A(N), made by Kyoeisha Chemical Co., Ltd.),
2-methacryloyloxyethyl acid phosphate (Light Ester P-1M, made by
Kyoeisha Chemical Co., Ltd.), Light Ester P-2M, made by Kyoeisha
Chemical Co., Ltd., and KAYAMER (registered trademark) PM-2, made
by Nippon Kayaku Co., Ltd.
Specific examples of the surfactant include a cationic surfactant,
an anionic surfactant and a nonionic surfactant.
Specific examples of the ionic surfactant include a titanate
compound, imidazoline, a quaternary ammonium salt, alkylamine
oxide, a polyamine derivative, a polyoxyethylene-polyoxypropylene
condensate, polyethylene glycol and an ester thereof, sodium lauryl
sulfate, ammonium lauryl sulfate, amines lauryl sulfate,
alkyl-substituted aromatic sulfonate, alkyl phosphate, an aliphatic
or aromatic sulfonic acid-formalin condensate, laurylamidopropyl
betaine, laurylaminoacetic acid betaine, polyethylene glycol fatty
acid ester, polyoxyethylene alkylamine, perfluoroalkyl sulfonate
and perfluoroalkyl carboxylate.
Specific examples of kinds of nonionic surfactants include
vinyl-based, silicone-based, fluorine-based and hydrocarbon-based
surfactants, and the vinyl-based surfactant is preferred.
Specific examples of the vinyl-based nonionic surfactant include
one or more surfactants selected from polyalkyl acrylate, polyalkyl
methacrylate, polyalkyl vinyl ether, polybutadiene, polyolefin and
polyvinyl ether.
Specific examples of the silicone-based nonionic surfactant include
polydimethylsiloxane, polyphenylsiloxane, specifically modified
siloxane, fluorine-modified siloxane and surface-treated
siloxane.
Specific examples of the fluorine-based nonionic surfactant include
a fluorine polymer.
Specific examples of the hydrocarbon-based nonionc surfactant
include polyethylene, polypropylene, polyisobutylene, paraffin,
liquid paraffin, chlorinated polypropylene, chlorinated paraffin
and chlorinated liquid paraffin.
Specific examples include a silicone-based nonionic surfactant
described in paragraph 0196 of JP 2011-246365 A, a fluorine-based
nonionic surfactant described in paragraph 0197 of the same
gazette, a nonionic surfactant containing an acrylic polymer as a
main component as described in paragraph 0199 of the same gazette,
and a fluorine-based nonionic surfactant or a silicone-based
nonionic surfactant described in paragraph 0019 of JP 2009-242563
A, or TEGO Flow 300, TEGO Flow 370 and TEGO Flow ZFS460 (made by
Evonik Industries AG) being vinyl-based nonionic surfactants.
The surfactant may be used alone or in combination of two or more
surfactants.
Among the surfactants, the vinyl-based surfactant being the
nonionic surfactant has a lower degree of segregation on a surface
of the paint film (without excessive localization) in comparison
with the silicone-based or fluorine-based nonionic surfactant, and
therefore is considered to be advantageous in suppressing the
alignment defect and developing the tilt alignment. Among the
vinyl-based surfactants, polyalkyl acrylate (acrylic polymer),
polyalkyl methacrylate or the like is further preferred.
Specific examples of the vinyl-based surfactant containing the
acrylic polymer or acrylic copolymer as the main component include
Polyflow series (Polyflow No. 7, No. 50 E, No. 50 EHF, No. 54 N,
No. 75, No. 77, No. 85, No. 85 HF, No. 90, No. 90 D-50, No. 95 or
No. 99 C) (made by Kyoeisha Chemical Co., Ltd.), TEGO Flow series
(TEGO Flow 300, 370, or ZFS 460) (made by Evonik Industries AG) and
BYK series (BYK 350, 352, 354, 355, 356, 358N, 361N, 381, 392, 394,
3441 or 3440) (made by BYK Japan KK).
Addition of the surfactants as described above presumably causes
moderate suppression of the homeotropic alignment on a side of an
air interface, and alignment of directions of raising liquid
crystal molecules from the interface in one direction. Therefore,
the alignment defect can be presumably suppressed. Moreover, the
surfactant is effective in facilitating control of uniformity of
the directions of raising the liquid crystal molecules in the tilt
alignment, uniform application of the composition onto the support
substrate or the like.
Moreover, in order to optimize applicability to the substrate, a
surfactant classified as a (substrate) wetting agent may be
simultaneously used in the range in which the tilt alignment is not
affected. The wetting agent is effective in decreasing surface
tension of the polymerizable liquid crystal solution and improving
applicability to a coating substrate. Specific examples of such a
wetting agent include Polyflow series (KL-100, KL-700, LE-604, 605,
606), TEGO Twin series (4000) (made by Evonik Industries AG) and
TEGO Wet series (KL245, 250, 260, 265 and 270, 280, 500, 505, 510,
520) (made by Evonik Industries AG).
The surfactant may have a polymerizable group in order to cause
integration with the polymerizable liquid crystal compound.
Specific examples of the polymerizable group to be introduced into
the surfactant include an ultraviolet light reaction-type
functional group and a thermally polymerizable functional group.
From a viewpoint of reactivity with the polymerizable liquid
crystal compound, the ultraviolet light reaction-type functional
group is preferred. A preferred ratio of the surfactant is in the
range of approximately 0.0001 to approximately 0.05, and further
preferably, in the range of approximately 0.0003 to approximately
0.03 in terns of a weight ratio based on the total weight of
component (A) and component (B), although the ratio is different
depending on a kind of surfactant, a composition ratio of the
compositions or the like.
In order to optimize a rate of polymerization of the polymerizable
liquid crystal composition, a publicly known photopolymerization
initiator may be used. A preferred amount of addition of the
photopolymerization initiator is approximately 0.0001 to
approximately 0.20 in terms of the weight ratio based on the total
weight of component (A) and component (B). A further preferred
weight ratio is in the range of approximately 0.001 to
approximately 0.15. A still further preferred ratio is in the range
of approximately 0.01 to approximately 0.15.
Specific examples of the photopolymerization initiator include
2-hydroxy-2-methyl-1-phenylpropane-1-one (Darocur (registered
trademark) 1173), 1-hydroxycyclohexylphenyl ketone,
2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure (registered
trademark) 651), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184),
Irgacure 127, Irgacure 500 (mixture of Irgacure 184 and
benzophenone), Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure
379, Irgacure 754, Irgacure 1300, Irgacure 819, Irgacure 1700,
Irgacure 1800, Irgacure 1850, Irgacure 1870, Darocur 4265, Darocur
MBF, Darocur TPO, Irgacure 784, Irgacure 754, Irgacure OXE01,
Irgacure OXE02, AdekaArkls NCI-831, Adeka Arkls NCI-930 and Adeka
Optomer N-1919. The photopolymerization initiator may be used alone
or in combination of two or more initiators. Both of Darocur and
Irgacure described above are names of products sold by BASF Japan,
Ltd. Both of Adeka Arkls and Adeka Optomer are names of products
sold by ADEKA Corporation. To the initiators, a publicly known
sensitizer (isopropylthioxanthone, diethylthioxanthone,
ethyl-4-dimethylaminobenzoate (Darocur EDB),
2-ethylhexyl-4-dimethylaminobenzoate (Darocur EHA) and so forth)
may be added.
Other specific examples of the photoradical polymerization
initiator include p-methoxyphenyl-2,4-bis (trichloromethyl)
triazine, 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole,
9-phenylacridine, 9,10-benzophenazine, a benzophenone-Michler's
ketone mixture, a hexaarylbiimidazole-mercaptobenzimidazole
mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one,
benzyldimethylketal,
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, a
2,4-diethylxanthone-methyl p-dimethylaminobenzoate mixture and a
benzophenone-methyltriethanolamine mixture.
When a compound has (R.sup.61--F) to (R.sup.61--B) as the
polymerizable group upon using the compound represented by formula
(6), a publicly known photocationic polymerization initiator may be
used. A preferred amount of addition of the photocationic
polymerization initiator is approximately 0.0001 to approximately
0.1 in terms of the weight ratio based on the total weight of the
cationic polymerization compound. A further preferred weight ratio
is approximately 0.001 to approximately 0.07.
Specific examples of trade names of the photocationic
polymerization initiator include CPI series (CPI-100P, 200K) made
by San-Apro Ltd., Cyracure UVI-6990, Cyracure UVI-6974 and Cyracure
UVI-6992 as UCC product, AdekaOptomer SP series (SP-150, SP-170,
SP-171, SP-056, SP-066, SP-130, SP-140, SP-082, SP-103, SP-601,
SP-606 and SP-701), made by ADEKA Corporation, PHOTOINITIATOR 2074,
made by Rhodia, Ltd., Irgacure 250, 270 and 290, made by BASF Japan
Ltd., WPI series and WPAG series, made by Wako Pure Chemical
Industries, Ltd., UV-9380C, made by GE Silicones, and also TPS
series, TAZ series, DPI series, BPI series, MDS series, DTS series,
SI series, PI series, NDI series, PAI series, NAI series, NI
series, DAM series, MBZ series, PYR series, DNB series and NB
series, made by Midori Kagaku Co., Ltd.
When a salt is predicted to be generated to cause polymerization
inhibition during simultaneous use of the radical polymerization
initiator and a photo-acid generator, a change of the photo-acid
generator to a photo-base generator is recommended. Specific
examples of trade names of the photo-base generator include WPBG
series (WPBG-018, WPBG-027, WPBG-082, WPBG-140, WPBG-165, WPBG-166,
WPBG-167, WPBG-168, WPBG-172 and WPBG-266), made by Wako Pure
Chemical Industries, Ltd.
A thermal polymerization initiator may be used in the invention.
Specific examples of trade names include Adeka Opton series
(CP-66), made by ADEKA Corporation, and San-Aid (main agent) SI-60,
SI-80, SI-100, SI-110, SI-145, SI-150, SI-160 and SI-180, and
San-Aid (auxiliary agent), SI, made by Sanshin Chemical Industry
Co., Ltd. The initiators may be simultaneously used with the
photoradical initiator and the photocation polymerization
initiator, or with the photoradical initiator.
Mechanical characteristics of the optical anisotropic film can be
controlled by adding one kind or two or more kinds of chain
transfer agents to the polymerizable liquid crystal composition. A
length of a polymer chain or a length of two crosslinked polymer
chains in a polymer film can be controlled by using the chain
transfer agent. Both lengths can also be simultaneously controlled.
When an amount of the chain transfer agent is increased, the length
of the polymer chain decreases. Specific examples of preferred
chain transfer agents include a thiol compound and a styrene
dimer.
Specific examples of monofunctional thiol include dodecanethiol and
2-ethylhexyl-(3-mercaptopropionate). Specific examples of
polyfunctional thiol include
trimethylolpropanetris(3-mercaptopropionate),
pentaerythritoltetrakis(3-mercaptopropionate),
1,4-bis(3-mercaptobutyryloxy)butane (Karenz MT BD1),
pentaerythritoltetrakis(3-mercaptobutylate) (Karenz MTPE1) and
1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione
(Karenz MT NR1). "Karenz" is a trade name of products from Showa
Denko K.K. Specific examples of a thiol compound other than the
compounds described above include a thiol compound described in
paragraphs 0042 to 0043 in WO 2013/080855 A and a compound
described in 11.sup.th line on p. 23 to 27.sup.th line on p. 24 in
WO 2008/077261 A. Specific examples of the styrene dimer include
.alpha.-methylstyrene dimer (2,4-diphenyl-4-methyl-1-pentene) and
1,1-diphenylethylene. Moreover, Quinoexter QE-2014 can also be
utilized. "Quinoexter" is a trade name of products from Kawasaki
Kasei Chemicals Ltd.
A polymerization inhibitor can be added to the polymerizable liquid
crystal composition in order to prevent polymerization start during
storage. A publicly known polymerization inhibitor can be used, and
preferred examples include 2,5-di(t-butyl)hydroxytoluene (BHT),
hydroquinone, Methyl Blue, diphenylpicryl hydrazide (DPPH),
benzothiazine, 4-nitrosodimethylaniline (NIDI) and
o-hydroxybenzophenone. The polymerization inhibitor may be used
alone, or in combination of two or kinds.
An oxygen inhibitor can also be added in order to improve storage
stability of the polymerizable liquid crystal composition. A
radical generated within the composition reacts with oxygen in an
atmosphere and yields a peroxide radical by which an unwanted
reaction with the polymerizable compound is promoted. The oxygen
inhibitor is preferably added in order to prevent such a reaction.
Specific examples of the oxygen inhibitor include phosphate
esters.
In order to further improve weather resistance of the polymerizable
liquid crystal composition, an ultraviolet light absorber, a light
stabilizer (radical scavenger), an antioxidant and so forth may be
added. The additives may be used alone or in combination of two or
more of kinds. Specific examples of the ultraviolet light absorber
include Tinuvin PS, Tinuvin P, Tinuvin 99-2, Tinuvin 109, Tinuvin
213, Tinuvin 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin
384-2, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin
400, Tinuvin 405, Tinuvin 460, Tinuvin 479, Tinuvin 5236, ADK STAB
LA-32, ADK STAB LA-34, ADK STAB LA-36, ADK STAB LA-31, ADK STAB
1413 and ADK STAB LA-51. "Tinuvin (registered trademark)" is a
registered trademark of product from CIBA Holding Incorporated, and
a trade name of products from BASF Japan Ltd. Moreover, "ADK STAB
(registered trademark)" is a trade name of products from ADEKA
Corporation.
Specific examples of the light stabilizer include Tinuvin 111 FDL,
Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622,
Tinuvin 770, Tinuvin 765, Tinuvin 780, Tinuvin 905, Tinuvin 5100,
Tinuvin 5050 and 5060, Tinuvin 5151, Chimassorb 119 FL, Chimassorb
944 FL, Chimassorb 944 LD, ADK STAB LA-52, ADK STAB LA-57, ADK STAB
LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB
LA-77, ADK STAB LA-82, ADK STAB LA-87, Cyasorb UV-3346, Uvinul
4050H, Uvinul 4077H, Uvinul 4092H, Uvinul 5050H and Uvinul 5062H,
made by Cytec Industries Inc., and Good-Rite UV-3034, made by
Goodrich Corporation. "Chimassorb (registered trademark)" and
Uvinul are trade names of products from BASF Japan Ltd.
Specific examples of the antioxidant include ADK STAB AO-20, AO-30,
AO-40, AO-50, AO-60 and AO-80, made by ADEKA Corporation, Sumilizer
(registered trademark) BHT, Sumilizer BBM-S and Sumilizer GA-80
sold by Sumitomo Chemical Co., Ltd., and Irganox (registered
trademark) 1076, Irganox 1010, Irganox 3114 and Irganox 245 sold by
BASF Japan Ltd. Commercial items thereof may also be used.
Alternatively, an antioxidant described in paragraph 0008 to
paragraph 0014 in JP 2008-44989 A may also be used.
In order to control adhesion with the support substrate, a silane
coupling agent may be further added to the polymerizable liquid
crystal composition. Specific examples of the silane coupling agent
include vinyltrialkoxysilane, 3-aminopropyltrialkoxysilane,
N-(2-aminoethyl)3-aminopropyltrialkoxysilane,
N-(1,3-dimethylbutylidene)-3-triethoxysilyl-1-propanamine,
3-triethoxysilyl-N-(1,3-dimethylbutylidene),
3-glycidoxypropyltrialkoxysilane, 3-chlorotrialkoxysilane and
3-methacryloxypropyltrialkoxysilane. Another example includes
dialkoxymethylsilane in which one of alkoxy groups (three) in the
compounds is replaced by methyl. A preferred silane coupling agent
includes 3-aminopropyltriethoxysilane. The silane coupling agent
may be used alone, or two or more of the silane coupling agent may
be mixed and used.
In order to provide the polymerizable liquid crystal composition
with polarization characteristics or fluorescence characteristics,
a dichroic dye or a fluorescent dye may be further added thereto.
The dichroic dye preferably includes (1) a dye having a high
dichroic ratio, (2) a dye having a high absorption coefficient in a
direction parallel to a molecule long axis, or (3) a dye having a
high compatibility or solubility with the polymerizable liquid
crystal composition. For example, a dye used in a guest-host liquid
crystal display device, such as anthraquinone dyes or azo dyes can
be used alone or in combination thereof. Moreover, the dichroic dye
may have a polymerizable group.
A preferred amount of addition of the dichroic dye is approximately
0.01 to approximately 0.50 in terms of the weight ratio based on
the total weight of component (A) and component (B). A further
preferred weight ratio is in the range of approximately 0.01 to
approximately 0.40. A still further preferred ratio is in the range
of approximately 0.01 to approximately 0.30. Specific examples of
the dichroic dye include SI-486, SI-426, SI-483, SI-412 and SI-428
as sold by Mitsui Fine Chemicals, Inc., and G-205, G-206, G-207,
G-241, G-472, LSB-278 and LSB-335 as sold by Nagase & Co., Ltd.
Commercial items thereof may also be used.
The polymerizable liquid crystal composition of the invention can
be directly applied to a surface of the support substrate. However,
in order to facilitate coating, the polymerizable liquid crystal
composition may be diluted with a solvent as long as the solvent
does not erode the support substrate. The solvent may be used alone
or in combination of two or more kinds. Specific examples of the
solvent include an ester solvent, an amide solvent, an alcohol
solvent, an ether solvent, a glycol monoalkyl ether solvent, an
aromatic hydrocarbon solvent, a halogenated aromatic hydrocarbon
solvent, an aliphatic hydrocarbon solvent, a halogenated aliphatic
hydrocarbon solvent, an alicyclic hydrocarbon solvent, a ketone
solvent and an acetate solvent.
Preferred examples of the ester solvent include alkyl acetate
(methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate,
butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl
acetate and isopentyl acetate), cyclohexyl acetate, ethyl
trifluoroacetate, alkyl propionate (methyl propionate, methyl
3-methoxypropionate, ethyl propionate, propyl propionate and butyl
propionate), alkyl butyrate (methyl butyrate, ethyl butylate, butyl
butyrate, isobutyl butyrate and propyl butyrate), dialkyl malonate
(diethyl malonate), alkyl glycolate (methyl glycolate and ethyl
glycolate), alkyl lactate (methyl lactate, ethyl lactate, isopropyl
lactate, n-propyl lactate, butyl lactate and ethylhexyl lactate),
monoacetin, .gamma.-butyrolactone and .gamma.-valerolactone.
Preferred examples of the amide solvent include
N-methyl-2-pyrrolidone, N,N-dimethylacetamide,
N-methylpropionamide, N, N-dimethylformamide, N,N-diethylformamide,
N,N-diethylacetamide, N,N-dimethylacetamide dimethylacetal,
N-methylcaprolactam and dimethylimidazolidinone.
Preferred examples of the alcohol solvent include methanol,
ethanol, 1-propanol, 2-propanol, l-methoxy-2-propanol, diacetone
alcohol, t-butyl alcohol, sec-butyl alcohol, butanol,
2-ethylbutanol, n-hexanol, n-heptanol, n-octanol, 1-dodecanol,
ethylhexanol, 3,5,5-trimethyl hexanol, n-amyl alcohol,
hexafluoro-2-propanol, glycerol, ethylene glycol, diethylene
glycol, triethylene glycol, tetraethylene glycol, propylene glycol,
dipropylene glycol, tripropylene glycol, hexylene glycol,
1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol,
2,4-pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol,
cyclohexanol and methylcyclohexanol.
Preferred examples of the ether solvent include ethylene glycol
dimethyl ether, diethylene glycol dimethyl ether, bis (2-propyl)
ether, 1,3-dioxolane, 1,4-dioxane, cyclopentyl methyl ether and
tetrahydrofuran (THF).
Preferred examples of the glycol monoalkyl ether solvent include
ethylene glycol monoalkyl ether (ethylene glycol monomethyl ether
and ethylene glycol monobutyl ether), diethylene glycol monoalkyl
ether (diethylene glycol monoethyl ether), triethylene glycol
monoalkyl ether, propylene glycol monoalkyl ether (propylene glycol
monobutyl ether), dipropylene glycol monoalkyl ether (dipropylene
glycol monomethyl ether), ethylene glycol monoalkyl ether acetate
(ethylene glycol monobutyl ether acetate), diethylene glycol
monoalkyl ether acetate (diethylene glycol monoethyl ether
acetate), triethylene glycol monoalkyl ether acetate, propylene
glycol monoalkyl ether acetate (propylene glycol monomethyl ether
acetate, propylene glycol monoethyl ether acetate and propylene
glycol monobutyl ether acetate), dipropylene glycol monoalkyl ether
acetate (dipropylene glycol monomethyl ether acetate) and
diethylene glycol methyl ethyl ether.
Preferred examples of the aromatic hydrocarbon solvent include
benzene, toluene, xylene, anisole, p-cymene, mesitylene,
ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene,
t-butylbenzene, s-butylbenzene, n-butylbenzene, a terpene
derivative (1,4-cineole, 1,8-cineole, D-limonene, D-limonene oxide,
p-menthane, .alpha.-pinene, .beta.-pinene, .gamma.-terpinene,
terpineol and tetralin. Preferred examples of the halogenated
aromatic hydrocarbon solvent include chlorobenzene.
Preferred examples of the aliphatic hydrocarbon solvent include
hexane and heptane. Preferred examples of the halogenated aliphatic
hydrocarbon solvent include chloroform, dichloromethane, carbon
tetrachloride, dichloroethane, trichloroethylene and
tetrachloroethylene. Specific preferred examples of the alicyclic
hydrocarbon solvent include cyclohexane, methylcyclohexane and
decalin.
Preferred examples of the ketone solvent include acetone, methyl
ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone,
cyclopentanone and methyl propyl ketone.
Preferred examples of the acetate solvent include ethylene glycol
monomethyl ether acetate, propylene glycol monomethyl ether
acetate, propylene glycol monoethyl ether acetate, methyl
acetoacetate and 1-methoxy-2-propyl acetate.
From a viewpoint of solubility of the polymerizable liquid crystal
compound, use of the amide solvent, the aromatic hydrocarbon or the
ketone solvent is preferred, and when a boiling point of the
solvent is taken into consideration, simultaneous use of the ester
solvent the alcohol solvent, the ether solvent and the glycol
monoalkyl ether solvent is also preferred. Selection of the solvent
is not particularly limited, but when the plastic substrate is used
as the support substrate, drying temperature is required to be
decreased for preventing substrate deformation, and the solvent is
required to cause no substrate erosion. Preferred examples of the
solvent used in such a case include an aromatic hydrocarbon
solvent, a ketone solvent, an ester solvent, an ether solvent, an
alcohol solvent, an acetate solvent and a glycol monoalkyl ether
solvent.
A ratio of the solvent in the solution of the polymerizable liquid
crystal composition is ordinarily in the range of approximately 0
to approximately 95% based on the total weight of the solution. A
lower limit of the range is set to a value determined in
consideration of a case where the support substrate is subjected to
erosion by the solvent. Then, an upper limit thereof is set to a
value determined in consideration of solution viscosity, solvent
cost, and productivity such as time and an amount of heat upon
evaporating the solvent. A ratio is preferably in the range of
approximately 0 to approximately 90%, and further preferably in the
range of approximately 0 to approximately 85%.
In the explanation below, the liquid crystal film obtained by
curing the polymerizable liquid crystal composition may be
occasionally referred to as the optical anisotropic film. The
optical anisotropic film can be formed in a manner described below.
First, the polymerizable liquid crystal composition or the solution
thereof is applied onto the support substrate, and the resulting
applied material is heated and dried to form the paint film. Next,
the paint film is irradiated with light to polymerize the
polymerizable liquid crystal composition and to immobilize nematic
alignment formed by the composition in the paint film in the liquid
crystal state.
Usable support substrates are glass and a plastic film. Specific
examples of the plastic film include a film of polyimide,
polyamideimide, polyamide, polyetherimide, polyether ether ketone,
polyether ketone, polyketone sulfide, polyethersulfone,
polysulfone, polyphenylene sulfide, polyphenylene oxide,
polyethylene terephthalate (PET), polybutylene terephthalate,
polyethylene naphthalate, polyacetal, polycarbonate, polyarylate,
an acrylic resin, polyvinyl alcohol, polypropylene, cellulose,
triacetyl cellulose and a partially saponified product thereof, an
epoxy resin, a phenol resin or a cycloolefin resin.
Specific examples of the cycloolefin resin include a norbornene
resin and a dicyclopentadiene resin, but are not limited thereto.
Among the resins, a resin having no unsaturated bond or a resin in
which an unsaturated bond is hydrogenated is suitably used.
Specific examples include a hydrogenated product of a ring-opened
(co)polymer of one kind or two or more kinds of norbornene
monomers, an addition (co)polymer of one kind or two or more kinds
of norbornene monomers, an addition copolymer of a norbornene
monomer and an olefin monomer (ethylene, .alpha.-olefin), an
addition copolymer of a norbornene monomer and a cycloolefin
monomer (cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene)
and a modified product thereof. Specific examples include ZEONEX
(registered trademark), ZEONOR (registered trademark, made by Zeon
Corporation), ARTON (made by JSR Corporation), TOPAS (registered
trademark, made by Ticona GmbH), APEL (registered trademark, made
by Mitsui Chemicals, Inc.), S-SINA (registered trademark, made by
Sekisui Chemical Co., Ltd.) and OPTOREZ (made by Hitachi Chemical
Co., Ltd.).
The plastic film may be the uniaxially oriented film or the
biaxially oriented film. The plastic film may be subjected to, for
example, hydrophilization treatment such as corona treatment or
plasma treatment, or surface treatment such as hydrophobization
treatment. A method for hydrophilization treatment is not
particularly restricted, but corona treatment or plasma treatment
is preferred, and a particularly preferred method is plasma
treatment. For the plasma treatment, a method described in JP
2002-226616 A, JP 2002-121648 A or the like may be applied.
Moreover, an anchor coat layer may be formed for improving adhesion
between a liquid crystal film and a plastic film. Such an anchor
coat layer may be formed of any of an inorganic material or an
organic material without any problem, as long as the material
improves adhesion between the liquid crystal film and the plastic
film. Moreover, the plastic film may be a laminated film. In place
of the plastic film, a material can also be used, such as a
metallic substrate of aluminum, iron or copper on a surface of
which slit-shaped grooves are formed, and a glass substrate of
alkaline glass, borosilicate glass or flint glass to a surface of
which etching processing is applied in a slit shape.
Prior to forming the paint film of the polymerizable liquid crystal
composition, physical or mechanical surface treatment by rubbing
may be applied on the support substrate such as the glass and the
plastic film. Alternatively, photo alignment treatment by polarized
ultraviolet light may be applied. When the tilt alignment is
formed, the surface treatment by rubbing may be directly applied to
the support substrate, or the alignment film may be arranged
beforehand on the support substrate, and then rubbing treatment may
be applied to the alignment film.
Specific examples of the alignment film include a polyimide film, a
polyamide film and a polyvinyl alcohol film. A particularly
preferred alignment film includes a polyimide film. In order to
increase a mean tilt angle, an alignment film may be utilized in
which a side chain component is introduced into the polyimide. An
arbitrary method can be employed for the rubbing treatment, but a
method is ordinarily applied by winding a rubbing fabric formed of
a raw material such as rayon, cotton and polyamide around a
metallic roll or the like to move the roll while rotating the roll
in a state in contact with a support substrate or an alignment
layer, or moving a support substrate side while fixing the roll.
Depending on a kind of the support substrate, silicon oxide is
obliquely vapor-deposited to allow provision of alignment ability
on a surface thereof. In case of using a photo alignment film, the
substrate only needs to be tilted upon irradiating the substrate
with polarized ultraviolet light.
Upon coating the polymerizable liquid crystal composition or the
solution thereof, specific examples of an application method for
obtaining uniform thickness include a spin coating method, a micro
gravure coating method, a gravure coating method, a wire bar
coating method, a dip coating method, a spray coating method, a
meniscus coating method and a die coating method. In particular,
the wire bar coating method or the like in which shear stress is
applied to the liquid crystal compound during application may be
applied in controlling alignment of the polymerizable liquid
crystal material without applying surface treatment of the
substrate by rubbing or the like.
Upon preparing the solution of the polymerizable liquid crystal
composition, selection is made from a solvent having capability of
dissolving the polymerizable liquid crystal composition, and also
maintaining uniform alignment properties of a tilt alignment layer
obtained from the polymerizable liquid crystal composition of the
invention and minimizing solvent damage to the support substrate.
Specific examples of such a solvent include the solvent described
above used upon preparing the solution of the polymerizable liquid
crystal composition. Then, an amount used is also set up within the
range in which the uniform alignment the polymerizable liquid
crystal composition is maintained and damage to the support
substrate is minimized.
Upon coating the polymerizable liquid crystal composition of the
invention or the solution thereof, when the solvent is contained,
the solvent is removed to allow formation of a polymerizable liquid
crystal layer, namely, a polymerizable liquid crystal composition
layer having a uniform thickness on the support substrate.
Conditions on solvent removal are not particularly limited. Drying
only needs to be performed until the solvent is substantially
removed and flowability of the paint film of the polymerizable
liquid crystal composition is lost. The solvent can be removed
applying air drying at room temperature, drying on a hot plate,
drying in a drying furnace, blowing of warm air or hot air or the
like.
Depending on a kind and a composition ratio of the compounds used
for the polymerizable liquid crystal composition, the nematic
alignment of the polymerizable liquid crystal composition in the
paint film is completed in a process of drying of the coating film
in some cases. Therefore, the paint film through a drying step can
be provided for a polymerization step without passing through a
heat treatment step to be described later.
A preferred range of temperature and time upon applying heat
treatment to the paint film, a wavelength of light used for
irradiation with light, an amount of light to be irradiated from a
light source or the like is different depending on a kind and a
composition ratio of the compounds used for the polymerizable
liquid crystal composition, presence or absence of addition of the
photopolymerization initiator, an amount of addition thereof or the
like. Therefore, conditions of the temperature and the time of heat
treatment of the paint film, the wavelength of light used for
irradiation with light, and the amount of light to be irradiated
from the light source explained below represent only an approximate
range.
The heat treatment of the paint film is preferably applied on
conditions under which the solvent is removed and uniform alignment
properties of the polymerizable liquid crystal compound are
obtained. One example of the heat treatment method includes a
method for warming the paint film to temperature at which the
nematic alignment is formed in the polymerizable liquid crystal
compound in the paint film. The nematic alignment may be formed by
changing the temperature of the paint film in a temperature range
in which the polymerizable liquid crystal compound shows a nematic
liquid crystal phase. The above method includes a method for
warming the paint film to a high temperature region in the
temperature range described above, thereby almost competing the
nematic alignment in the paint film, and then decreasing
temperature to form further-ordered alignment. Depending on the
conditions under which the uniform alignment properties of the
polymerizable liquid crystal composition is obtained, the heat
treatment may be applied at temperature equal to or higher than a
transition point temperature (clearing point temperature) from a
liquid crystal phase to an isotropic phase of the polymerizable
liquid crystal composition. According to the method, the paint film
is heated to temperature at which the paint film forms the
isotropic phase, and then cooling the film to temperature at which
the paint film forms the nematic alignment to form further-ordered
alignment.
Even when any one of the heat treatment methods described above is
applied, the heat treatment temperature is ordinarily approximately
room temperature (25.degree. C.) to approximately 150.degree. C. A
preferred temperature range is approximately room temperature
(25.degree. C.) to approximately 140.degree. C., a further
preferred range is approximately room temperature (25.degree. C.)
to approximately 130.degree. C., and a still further preferred
range is approximately room temperature (25.degree. C.) to
approximately 120.degree. C.
Heat treatment time is ordinarily approximately 5 seconds to
approximately 2 hours. A preferred range of the time is
approximately 10 seconds to approximately 40 minutes, and a further
preferred range is approximately 20 seconds to approximately 20
minutes. In order to increase the temperature of the layer formed
of the polymerizable liquid crystal composition to a predetermined
temperature, the heat treatment time is preferably adjusted to
approximately 5 seconds or more. In order to avoid a decrease in
productivity, the heat treatment time is preferably adjusted within
approximately 2 hours. Thus, the polymerizable liquid crystal layer
in which the tilt alignment is formed according to the invention is
obtained.
The nematic alignment state of the polymerizable liquid crystal
compound as formed in the polymerizable liquid crystal composition
layer is immobilized by polymerization of the polymerizable liquid
crystal compound by irradiation with light. A wavelength of light
used for irradiation with light is not particularly limited.
Electron beams, ultraviolet light, visible light, infrared light
(heat rays) or the like can be used. Ultraviolet light or visible
light is ordinarily sufficiently used. A range of wavelength is
ordinarily approximately 150 to approximately 500 nanometers. A
preferred range is approximately 250 to approximately 450
nanometers, and a further preferred range is approximately 300 to
approximately 400 nanometers. Specific examples of the light source
include a low-pressure mercury lamp (a germicidal lamp, a
fluorescence chemical lamp, a black light), a high-pressure
discharge lamp (a high-pressure mercury lamp, a metal halide lamp)
and a short arc discharge lamp (an ultrahigh pressure mercury lamp,
a xenon lamp and a mercury xenon lamp). Preferred examples of the
light source include a metal halide lamp, a xenon lamp, an
ultrahigh pressure mercury lamp and a high-pressure mercury lamp. A
wavelength region of the light source for irradiation may be
selected by installing a filter or the like between the light
source and the polymerizable liquid crystal composition layer,
thereby selecting the wavelength region to of the light source for
irradiation.
An amount of light to be irradiated from the light source is
ordinarily approximately 2 to approximately 5,000 mJ/cm.sup.2. A
preferred range of the amount of light is approximately 10 to
approximately 3,000 mJ/cm.sup.2, and a further preferred range is
approximately 100 to approximately 2,000 mJ/cm.sup.2. Temperature
conditions during irradiation with light are preferably set up in a
manner similar to the conditions of the heat treatment temperature
described above. Moreover, an atmosphere of a polymerization
environment may include any of a nitrogen atmosphere, an inert gas
atmosphere and an air atmosphere, but a nitrogen atmosphere or an
inert gas atmosphere is preferred from a viewpoint of improving
curability.
When the polymerizable liquid crystal layer and the optical
anisotropic film obtained by polymerizing the polymerizable liquid
crystal layer using light, heat or the like according to the
invention are utilized for various optical devices, or applied to
an optical compensation device used for a liquid crystal display
apparatus, control of tilt angle distribution in a thickness
direction becomes significantly important.
One of the methods for controlling the tilt angle includes a method
for adjusting a kind, a composition ratio or the like of the liquid
crystal compounds used for the polymerizable liquid crystal
composition. The tilt angle can also be controlled by adding any
other component to the polymerizable liquid crystal compound. The
tilt angle of the optical anisotropic film can also be controlled
by a kind of solvent and a solute concentration in the
polymerizable liquid crystal composition, a kind and an amount of
addition of a surfactant to be added as one of the other
components, or the like.
The tilt angle of the optical anisotropic film can also be
controlled by a kind and rubbing conditions of the support
substrate or the polymer coating film, or by drying conditions or
heat treatment conditions of the paint film of the polymerizable
liquid crystal composition. When glass is used as the support
substrate and a polyimide rubbing alignment film is used as the
alignment film, drying temperature is adjusted to a vicinity of
temperature (clearing point) at which the polymerizable liquid
crystal changes to the isotropic phase, heating the liquid crystal
composition to a clearing point temperature or higher, thereby
allowing a decrease in the alignment defect in some cases.
Moreover, an irradiation atmosphere in a photopolymerization step
after alignment, temperature during irradiation, or the like also
affects the tilt angle of the optical anisotropic film. More
specifically, almost all the conditions in the process for
manufacturing the optical anisotropic film are considered to affect
the tilt angle to some extent.
Therefore, the polymerizable liquid crystal composition is
optimized, and simultaneously the conditions of the process for
manufacturing the optical anisotropic film are appropriately
selected, thereby allowing achievement of an arbitrary tilt
angle.
The tilt alignment means the state in which the alignment state
further rises from parallel to perpendicular as the alignment state
is further separated from the substrate. Examples of the tilt angle
in the tilt alignment include approximately 5 degrees to
approximately 85 degrees. The alignment state is obtained by
forming on the support substrate surface the paint film of the
polymerizable liquid crystal composition according to the invention
to which component (A) and component (B) are added on the alignment
film subjected to surface treatment such as rubbing treatment and
photo alignment treatment.
In order to control the high tilt angle, when a compound
represented by formula (1-1) and/or a compound represented by
formula (1-3) is used as component (A), 9-methylfluorene (more
specifically, either W.sup.2 or W.sup.3 is methyl and the other is
hydrogen) is preferably used fluorene structure. When a compound
represented by formula (1-2) is used, a compound in which W.sup.4
is methyl, alkyl having 1 to 7 carbons or alkoxy carbonyl
(--COOR.sup.b: R.sup.b is straight-chain alkyl having 1 to 7
carbons) is preferably used.
On the other hand, when both of W.sup.2 and W.sup.3 are methyl in a
compound represented by formula (1-1) or a compound represented by
formula (1-3), a melting point tends to increase. Thus, both
compounds are preferred for an application needing heat
resistance.
As component (B), a plurality of kinds of compounds represented by
formula (2-1) may be simultaneously used. R.sup.c in R.sup.1 as a
terminal group is preferably straight-chain alkyl having 1 to 10
carbons. R.sup.c is further preferably straight-chain alkyl having
1 to 6 carbons and R.sup.d is a single bond. Moreover, from a
viewpoint of liquid crystallinity and solubility in the solvent, q1
is preferably 1.
In order to reduce the alignment defect in the tilt alignment, a
surfactant may be added. Moreover, in order increase the tilt
angle, a compound represented by formula (3) and a compound
represented by formula (4) may be simultaneously used.
A suitable thickness of the optical anisotropic film is different
depending on retardation according to an objective device or
birefringence of the optical anisotropic film. Therefore, the range
thereof is quite difficult to be strictly determined, but a
preferred thickness of the optical anisotropic film is
approximately 0.05 to approximately 50 micrometers. A further
preferred range is approximately 0.1 to approximately 20
micrometers, and still further preferred range is approximately 0.5
to approximately 10 micrometers. A preferred haze value of the
optical anisotropic film is approximately 1.5% or less, and a
preferred transmittance is approximately 80% or more. A further
preferred haze value is approximately 1.0% or less, and a further
preferred transmittance is approximately 95% or more. The
transmittance preferably meets the conditions in a visible light
region.
The optical anisotropic film is effective as the optical
compensation device applied to the liquid crystal display device
(in particular, a liquid crystal display device of an active matrix
mode and a passive matrix mode). Specific examples of modes of the
liquid crystal display device suitable for using the optical
anisotropic film in the form of an optical compensation film
include an in-plane switching (IPS) mode, an optically compensated
birefringence (OCB) mode, a twisted nematic (TN) mode, a
supertwisted nematic (STN) mode, an electrically controlled
birefringence (ECB) mode, a hybrid aligned pneumatic (HAN) mode, a
deformation of aligned phase (DAP) mode, a color super homeotropic
(CSH) mode, a vertical aligned nematic/vertical aligned cholesteric
(VAN/VAC) mode, an optical mode interference (OMI) mode and a
super-birefringence effect (SBE) mode. The optical anisotropic film
can also be used as a phase retarder for a display device of a
guest-host mode, a ferroelectric mode and an antiferroelectric
mode. In addition, an optimum value of parameters such as a tilt
angle distribution in a thickness direction and thickness required
for the optical anisotropic film strongly depends on a kind and an
optical parameter of the liquid crystal display device to be
compensated, and an optical parameter thereof, and is different
depending on a type of the device.
The optical anisotropic film can be used also as an optical device
integrated with a polarizing plate or the like, and is arranged on
an outer surface of a liquid crystal cell in the above case. The
optical anisotropic film as the optical compensation device,
however, shows no or little impurity elution to the liquid crystal
filled in the cell, and therefore can be arranged on an inner
surface of the liquid crystal cell. For example, when a method
disclosed in JP 4899828 B (JP 2008-134530 A) is applied, a liquid
crystal display composition can be obtained in which an optical
compensation layer is formed in a liquid crystal cell. An optical
anisotropic film to which a dichroic dye is added has polarization
characteristics, and therefore when a method disclosed in, for
example, JP 4778192 B (JP 2004-535483 A), JP H11-337898 A, JP
H11-101964 A or WO 2005/45485 A, the optical anisotropic film can
be formed into a viewing angle control member.
It will be apparent to those skilled in the art that various
modifications and variations can be made in the invention and
specific examples provided herein without departing from the spirit
or scope of the invention. Thus, it is intended that the invention
covers the modifications and variations of this invention that come
within the scope of any claims and their equivalents.
The following examples are for illustrative purposes only and are
not intended, nor should they be interpreted to, limit the scope of
the invention.
EXAMPLES
In the following, the invention will be explained in detail by way
of Examples, but the invention is not limited to the Examples.
Evaluation methods in Examples are presented below.
Polymerization Conditions
Under a nitrogen atmosphere, a sample was irradiated with light
having an intensity of 20 mW/cm.sup.2 (365 nm) at room temperature
(25.degree. C.) for 30 seconds using a 250 W ultrahigh pressure
mercury lamp (made by Ushio, Inc.).
Confirmation of Liquid Crystal Alignment State
An optical anisotropic film obtained was interposed between two
polarizing plates arranged in a crossed Nicol state, and
observation light was irradiated from a direction perpendicular to
an optical anisotropic film surface (Incident angle: 0 degrees). A
change of transmitted light was observed by increasing the incident
angle from 0 degrees to 50 degrees, for example. A direction of
observation light was coincided with a direction of rubbing
alignment treatment (long axis direction of liquid crystals). When
transmission of light from a perpendicular direction was confirmed
to be maximum, and intensity of transmitted light was confirmed to
be symmetrical in right-left in the rubbing direction centering on
the perpendicular direction, the orientation state was judged to be
in homogeneous alignment (see FIG. 2) because a liquid crystal
alignment vector is parallel to a support substrate in the
homogeneous alignment. On the other hand, when a transmission of
light from a perpendicular direction was confirmed to be an
asymmetric change in right-left in the rubbing direction centering
on the perpendicular direction, the orientation state was judged to
be in tilt alignment (see FIG. 1) because the alignment vector of
the liquid crystal molecules was shown to be tilted relative to the
support substrate (glass substrate).
Measurement with Ellipsometer
The substrate having the liquid crystal film was irradiated with
light having a wavelength of 550 nm with Optipro Ellipsometer,
available from Shintech Co., Ltd. The retardation was measured by
decreasing the incident angle of the light with respect to the
optical anisotopic film surface from a perpendicular direction
(Incident angle 0 degree). The retardation is expressed by
.DELTA.n.times.d, wherein .DELTA.n represents the optical
anisotropy, and d represents the thickness of the optical
anisotropic film.
Compounds used are shown below.
##STR00079##
Compounds represented by formula (1-1-3) was prepared by a method
described in JP 2003-238491 A (JP 4036076 B).
A trans-form compound represented by formula (1-3-A2) was prepared
by a method described in JP 2012-177087 A.
A compound represented by formula (2-1-3) was prepared in a manner
similar to a method described in U.S. Pat. No. 4,248,754 B.
A compound represented by formula (5-1-3) was prepared in a manner
similar to a method described in Macromolecules, 26, 6132-6134
(1993).
A compound represented by formula (5-1-7) was prepared in a manner
similar to a method described in Makromol. Chem., 183, 2311-2321
(1982).
A compound represented by formula (6-1-12-1) was prepared by a
method described in JP 2011-246365 A.
Example 1
Preparation of Solution of Polymerizable Liquid Crystal Composition
(1)
Compound (1-1-3) and compound (2-1-3) were mixed in terms of a
weight ratio: compound (1-1-3): compound (2-1-3)=50:50. In terms of
a weight ratio based on the total weight of the mixture, 0.05 of
polymerization initiator Irgacure (registered trademark) 907, 0.001
of Irganox (registered trademark) 1076 and 0.002 of TEGOFLOW
(registered trademark) 370 (vinyl type surfactant) were added
thereto. Then, cyclopentanone was added thereto, and thus a
solution of polymerizable liquid crystal composition (1) was
obtained in which a concentration of the mixture of the
polymerizable liquid crystal compound was 35%.
Polyamic acid (Lixon Aligner: PIA-5580 for a high pre-tilt angle
(OCB alignment mode), made by JNC Corporation) was coated on a
glass substrate (Matsunami Slide Glass: S-1112), and after dring at
80.degree. C. for 3 minutes, the coated film was baked at
230.degree. C. for 30 minutes. Rubbing treatment was applied using
a rubbing fabric made from rayon (rubbing-treated alignment film).
Next, the solution of polymerizable liquid crystal composition (1)
was applied to the glass substrate with the rubbing-treated
alignment film by spin coating. The substrate was heated at
120.degree. C. for 2 minutes and cooled at room temperature for 2
minutes. The paint film from which the solvent was removed, was
polymerized with an ultraviolet light under a nitrogen flow to give
a liquid crystal film (optical anisotropic film). When the optical
anisotropic film obtained was interposed between two polarizing
plates arranged in a crossed Nicol state and the substrate was
placed into a dark state, no light leakage was observed, and thus
alignment was judged to be uniform. The measurement of retardation
of the optical anisotropic film provided the results shown in FIG.
1. The retardation profile was asymmetric, and thus the optical
anisotropic film revealed a tilt alignment and an average of tilt
angle was found to be 33 degrees.
Example 2
An optical anisotropic film was formed after obtaining a solution
of polymerizable liquid crystal composition (2) in a manner similar
to the method described in Example 1 except that adjustment was
made to a weight ratio: compound (1-1-3): compound (2-1-3)=30:70 in
the polymerizable liquid crystal composition (1) described in
Example 1. The measurement of retardation of the optical
anisotropic film revealed a tilt alignment having the same tendency
as in FIG. 1, and an average of tilt angle was found to be 40
degrees. When the optical anisotropic film obtained was interposed
between two polarizing plates arranged in a crossed Nicol state and
the substrate was placed in a dark state, no light leakage was
observed, and thus alignment was judged to be uniform.
Example 3
An optical anisotropic film was formed after obtaining a solution
of polymerizable liquid crystal composition (3) in a manner similar
to the method described in Example 1 except that adjustment was
made to a weight ratio: compound (1-1-3): compound (1-3-A2):
compound (2-1-3)=25:25:50 in the polymerizable liquid crystal
composition (1) described in Example 1. The measurement of
retardation of the optical anisotropic film revealed a tilt
alignment having the same tendency as in FIG. 1, and an average of
tilt angle was found to be 35 degrees. When the optical anisotropic
film obtained was interposed between two polarizing plates arranged
in a crossed Nicol state and the substrate was placed in a dark
state, no light leakage was observed, and thus alignment was judged
to be uniform.
Example 4
An optical anisotropic film was formed after obtaining a solution
of polymerizable liquid crystal composition (4) in a manner similar
to the method described in Example 1 except that mixing was made at
a weight ratio: compound (1-1-3): compound (2-1-3)=57:43, and then
in terms of a weight ratio based on the total amount of the
mixture, 0.43 of compound (5-1-3), 0.0067 of TEGOFLOW (registered
trademark) 370 (vinyl type surfactant), 0.05 of polymerization
initiator Irgacure (registered trademark) 907 and 0.001 of Irganox
(registered trademark) 1076 were added thereto. The measurement of
retardation of the optical anisotropic film revealed a tilt
alignment having the same tendency as in FIG. 1, and an average of
tilt angle was found to be 33 degrees. When the optical anisotropic
film obtained was interposed between two polarizing plates arranged
in a crossed Nicol state and the substrate was placed in a dark
state, no light leakage was abserved, and thus alignment was judged
to be uniform.
Comparative Example 1
An optical anisotropic film was formed after obtaining a solution
of polymerizable liquid crystal composition (4) in a manner similar
to the method described in Example 1 except that, in terms of a
weight ratio based on the total amount of the mixture, 1.00 of
compound (5-1-7), 0.0040 of TEGOFLOW (registered trademark) 370
(vinyl type surfactant), 0.05 of polymerization initiator Irgacure
(registered trademark) 907 and 0.001 of Irganox (registered
trademark) 1076 were added thereto. The measurement of retardation
of the optical anisotropic film provided the results shown in FIG.
2. The retardation profile was almost symmetrical, and therefore
the optical anisotropic film revealed almost a homogeneous
alignment and an average of tilt angle was found to be 5
degrees.
From the results described above, an optical anisotropic film
having a tilt alignment can be easily formed by using a
polymerizable liquid crystal compound having an ester moiety as a
terminal group, such as compound (2-1-3).
Example 5
An optical anisotropic film was formed after obtaining a solution
of polymerizable liquid crystal composition (5) in a manner similar
to the method described in Example 1 except that mixing was made at
a weight ratio: compound (1-1-3): compound (2-1-3)=37:63, and then
in terms of a weight ratio based on the total amount of the
mixture, 0.25 of compound (6-1-12-1), 0.0063 of TEGOFLOW
(registered trademark) 370 (vinyl type surfactant), 0.05 of
polymerization initiator Irgacure (registered trademark) 907 and
0.001 of Irganox (registered trademark) 1076 were added thereto.
The measurement of retardation of the optical anisotropic film
revealed a tilt alignment having the same tendency as in FIG. 1,
and an average of tilt angle was found to be 32 degrees. When the
optical anisotropic film obtained was interposed between two
polarizing plates arranged in a crossed Nicol state and the
substrate was placed in a dark state, no light leakage was
observed, and thus alignment was judged to be uniform.
Although the invention has been described and illustrated with a
certain degree of particularity, it is understood that the
disclosure has been made only by way of example, and that numerous
changes in the conditions and order of steps can be resorted to by
those skilled in the art without departing from the spirit and
scope of the invention.
INDUSTRIAL APPLICABILITY
A polymerizable liquid crystal composition of the invention
facilitates development of tilt alignment and allows yielding of an
optical anisotropic film having excellent tilt alignment properties
at low cost.
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